Om0c00647 Si 001

Supporting information
Influence of the N→Ru coordinate bond length on the

activity of the new type of Hoveyda-Grubbs olefin metathesis
catalysts containing a six-membered chelate ring possessing
a ruthenium−nitrogen bond
Pavel A. Kumandina, Alexandra S. Antonovaa, Kseniia A. Alekseevaa, Eugeniya V. Nikitinaa,
Roman A. Novikovb, Kirill A. Vasileva, Anna A. Sinelshchikovac, Mikhail S. Grigorievc, Kirill
B. Polyanskiia,*, Fedor I. Zubkova,*.
a
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University),
6 Miklukho-Maklaya St., Moscow 117198, Russian Federation
e-mail: Fedor I. Zubkov – fzubkov@sci.pfu.edu.ru
e-mail: Kirill B. Polyanskii − 1236tgp@mail.ru
b
V. A. Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, 32 Vavilov St., Moscow 119991,
Russian Federation
c
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr. 31,
bld. 4, Moscow 119071, Russian Federation
Contents
General information …………………………………………………………………………………………………………………………………………… S2

Experimental section …………………………………………………………………………………………………………………………………………. S2
Experimental part for X-ray analysis …………………………………………………………………………………………………………………. S8
References …………………………………………………………………………………………………………………………………………………………. S32
NMR spectrum data (PDF) ………………………………………………………………………………………………………………………………... S33
S2
General information
All experiments with ruthenium derivatives were performed under an inert atmosphere of dry argon, using
standard Schlenk techniques, dry and oxygen-free solvents. Toluene, dioxane and hexane were distilled over
sodium under argon atmosphere prior use. Chloroform and dichloromethane were distilled over P 2 O 5 . All reagents
were purchased from Sigma-Aldrich, and used as received. Styrene was distilled under Ar immediately prior to the
polymerization reaction. IR spectra were obtained in KBr pellets or in thin films using an Infralum FT-801 IR-
Fourier spectrometer. Mass spectra were taken on a Thermo Focus DSQ II GC-MS spectrometer (electron
ionization, 70 eV, ion source temperature 200 °C, gas chromatographic inlet with a Varian FactorFour VF-5ms
column) or on an Agilent 1100 series LC/MSD spectrometer with an API-ES/APCI ionization mode. Microanalyses
were performed for C, H, N on an Eurovector EA 3000 (CHNS) elemental analysis system and were within ±0.4%
of theoretical values.
1H, 13C and 31P NMR spectra were recorded on Jeol JNM-ECA 600 (600.1 MHz for 1H and 150.9 MHz for 13C) or
Bruker Avance 300 or 500 (300 or 500 MHz for 1H and 75.5 or 125.8 MHz for 13C) spectrometers using residual
solvent signals (7.26/77.0 ppm for 1H/13C CDCl 3 and 5.36/53.4 ppm for CH 2 Cl 2 ) or SiMe 4 as an internal standard.
Chemical shifts are given relative to SiMe 4 and referenced to the residual solvent signal.
13C{1H} and 13C-dept135-{1H} NMR spectra with {1H}-decoupling for ruthenium complexes were recorded using
90° "garp" composite pulse with 0.19 W power for broadband decoupling instead of commonly used "waltz16"
composite pulse. If "waltz16" composite pulse was still used, its power should be at least 1 W for effective full
decoupling of the 1J H–C coupling constant for CH=Ru signals at 311–317 ppm, and a sufficient cooling by strong air
flow should be used to avoid overheating of the sample. The same situation is for recording of 1H–13C HSQC and
edited-HSQC spectra, however in this case, 90° "garp" composite pulse with 1 W power for broadband {13C}-
decoupling in detected 1H-channel should be used in combination with sufficient cooling of the sample by strong
air flow. 1H NMR spectra, as well as 2D 1H–1H COSY, TOCSY, NOESY, and 1H–13C HMBC spectra, were recorded in
conventional mode. All necessary pulses and pulse sequences were used from Bruker library.
Experimental section
Synthesis of 1-(2-Ethenylbenzyl)pyrrolidine (4a)
To a solution of 1,2,3,4-tetrahydroisoquinoline (5.00 g, 38.0 mmol, 1.00 equiv) in the isopropyl alcohol (50 mL) 1,4-
dibromobutane (8.20 g, 38.0 mmol, 1.00 equiv) was added and the mixture was stirred at r.t. for 15 min. Then NaOH
(3.40 g, 84 mmol, 2.2 equiv) was added and reaction mixture was heated at reflux with continuous stirring for 2 h.
Solvent was evaporated under reduced pressure and Et 2 O (50 mL) was added to the residue and it was stirred for
another 30 min at r.t. Precipitate was filtered of and washed with Et 2 O (2 × 20 mL), filtrate was evaporated under
reduced pressure giving target product as viscous brown oil, which were further purified by column
chromatography on silica gel (hexane/EtOAc = 10:1 v/v) providing pure 1-(2-ethenylbenzyl)pyrrolidine (4a) as
slight-yellow oil (4.98 g, 26.6 mmol, 70%).
1H NMR (600 MHz, CDCl 3 ) δ 7.51 (dd, J = 2.0, 7.1 Hz, 1H, H-3-Ph), 7.34 (dd, J = 1.8, 7.5 Hz, 1H, H-6-Ph), 7.26-7.21 (m,
2H, H-4,5-Ph), 7.17 (dd, J = 10.6, 17.1 Hz, 1H, CH=CH 2 ), 5.65 (dd, J = 1.0, 17.1 Hz, 1H, H-2-trans), 5.30 (dd, J = 1.0, 10.6
Hz, 1H, H-2-cis), 3.69 (s, 2H, CH 2 N), 2.56-2.54 (m, 4H, H-2,5-Cyclo), 1.79-1.77 (m, 4H, H-3,4-Cyclo) ppm.
13C NMR (150 MHz, CDCl 3 ) δ 137.4, 136.5, 134.9, 130.0, 127.6, 127.3, 125.6, 115.4, 58.0, 54.3 (2C), 23.6 (2C) ppm.
S3
IR (KBr): 1626 cm–1. HR-MS [M + H]+ calcd. for C 13 H 18 N: 188.1434; found: 188.1428.
1-(2-Ethenylbenzyl)piperidine (4b): The synthesis method is the same as that of 4a. Product was purified by
column chromatography on silica gel (hexane/EtOAc = 10:1 v/v) to provide yellow oil (5.81 g, 28.9 mmol, 76%).
1H NMR (600 MHz, CDCl 3 ) δ 7.51 (dd, J = 1.5, 7.6 Hz, 1H, H-3-Ph), 7.28 (dd, J = 1.5, 7.2 Hz, 1H, H-6-Ph), 7.24-7.18 (m,
3H, H-4,5-Ph, CH=CH 2 ), 5.63 (dd, J = 1.5, 17.7 Hz, 1H, H-2-trans), 5.26 (dd, J = 1.5, 11.1 Hz, 1H, H-2-cis), 3.16 (s, 2H,
CH 2 NPh), 2.38-2.36 (m, 4H, H-2,6-Pip), 1.56-1.52 (m, 4H, H-3,5-Pip), 1.43-1.41 (m, 2H, H-4-Pip) ppm.
13C NMR (150 MHz, CDCl 3 ) δ 137.8, 135.9, 135.0, 130.0, 127.2, 127.1, 125.6, 115.0, 61.27, 54.6 (2C), 26.0 (2C), 24.5 ppm.
2-(2-Ethenylbenzyl)-2,3-dihydro-1H-isoindole (4c)
The synthesis method is the same as that of 4a. Product was purified by column chromatography on silica gel
(hexane/EtOAc = 10:1 v/v) to provide yellow oil (6.16 g, 26.2 mmol, 69%).
1H NMR (600 MHz, CDCl 3 ) δ 7.56 (dd, J = 1.5, 7.1 Hz, 1H, H-Ar), 7.38 (dd, J = 1.5, 7.1 Hz, 1H, H-Ar), 7.30-7.27 (m, 2H,
H-Ar), 7.24 (dd, J = 11.0, 17.1 Hz, 1H, CH=CH 2 ), 7.18 (br. s, 4H, H-Ar-Isoindole), 5.69 (dd, J = 1.5, 17.2 Hz, 1H, H-2-
trans), 5.30 (dd, J = 1.5, 11.1 Hz, 1H, H-2-cis), 3.96 (s, 2H, CH 2 N-exo-cycl), 3.94 (s, 4H, H-1,3-endo-cycl) ppm.
13C NMR (150 MHz, CDCl 3 ) δ 140.2, 137.5, 136.0, 134.6, 129.9, 127.9, 127.6, 127.5, 126.6, 125.7 (2C), 122.3 (2C), 115.5, 58.9
(2C), 57.8 ppm.
IR (KBr): 1626 cm–1. MS-HR (ESI+) [M + H]+ calcd. for C 17 H 18 N: 236.1434; found: 236.1431.
2-(2-Ethenylbenzyl)-1,2,3,4-tetrahydroisoquinoline (4d):
The synthesis method is the same as that of 4a. Product was purified by column chromatography on silica gel
(hexane/EtOAc = 10:1 v/v) to provide yellow oil (6.73 g, 28.0 mmol, 71%).
1H NMR (600 MHz, CDCl 3 ) δ 7.54 (dd, J = 1.5, 7.6 Hz, 1H, H-3-Ph(vinyl)), 7.36 (dd, J = 1.5, 7.1 Hz, 1H, H-8-Ph), 7.28-
7.22 (m, 3H, H-Ar), 7.12-7.08 (m, 3H, 2H-Ar, CH=CH 2 ), 6.99-6.97 (m, 1H, H-6-Ph(vinyl)), 5.65 (dd, J = 1.5, 17.6 Hz,
1H, H-2-trans), 5.26 (dd, J = 1.5, 11.1 Hz, 1H, H-2-cis), 3.69 (s, 2H, CH 2 N-exo-cycl), 3.64 (s, 2H, CH 2 N-endo-cycl (H-
1)), 2.87 (br.t, J = 6.0 Hz, 2H, H-3), 2.73 (t, J = 6.0 Hz, 2H, H-4) ppm.
13C NMR (150 MHz, CDCl 3 ) δ 138.0, 135.5, 135.2, 134.9, 134.7, 130.4, 128.8, 127.54, 127.51, 126.7, 126.1, 125.8, 125.6, 115.5,
60.5, 56.3, 50.6, 29.4 ppm.
4-(2-Ethenylbenzyl)morpholine (4e): The synthesis method is the same as that of 4a. Product was purified by
column chromatography on silica gel (hexane/EtOAc = 10:1 v/v) to provide yellow oil (6.01 g, 29.6 mmol, 78%).
1H NMR (600 MHz, CDCl 3 ) δ 7.53 (dd, J = 1.5, 7.6 Hz, 1H, H-3-Ph), 7.26-7.18 (m, 4H, H-4,5,6-Ph and CH=CH 2 ), 5.65
(dd, J = 1.5, 17.7 Hz, 1H, H-2-trans), 5.29 (dd, J = 1.5, 11.1 Hz, 1H, H-2-cis), 3.67 (t, J = 4.8 Hz, 4H, CH 2 OCH 2 ), 3.50 (s,
2H, ArCH 2 N), 2.43 (br.t, 4H, CH 2 NCH 2 ) ppm.
13C NMR (150 MHz, CDCl 3 ) δ 138.0, 135.0, 134.9, 130.6, 127.7, 127.5, 125.8, 115.4, 67.2 (2C), 61.2, 53.7 (2C) ppm.
IR (KBr): 1626 cm–1. HR-MS [M + H]+ calcd. for C 13 H 18 NO: 204.1383; found: 204.1387.
1-Methyl-4-(2-vinylbenzyl)piperazine (4f): The synthesis method is the same as that of 4a. Product was purified
by column chromatography on silica gel (hexane/EtOAc = 10:1 v/v) to provide yellow oil (5.09 g, 23.6 mmol, 62%).
1H NMR (600 MHz, CDCl 3 ) δ 7.52 (d, J = 7.3 Hz, 1H, H-3), 7.27-7.18 (m, 4H, 4,5,6-Ph, CH=CH 2 ), 5.64 (d, J = 17.6 Hz,
1H, H-2-trans), 5.28 (dd, J = 11.1 Hz, 1H, H-2-cis), 3.51 (s, 2H, N-CH 2 ), 2.46 (br. s, 8H, 2,3,4,6-H-pip), 2.27 (s, 3H, N-
Me) ppm.
S4
13C NMR (151 MHz, CDCl 3 ) δ 137.9, 135.4, 134.9, 130.5, 127.5, 127.4, 125.7, 115.3, 60.7, 55.3 (2C), 53.2 (2C), 46.2 ppm. IR
(KBr): 1624 cm–1. HR-MS [M + H]+ calcd. for C 14 H 21 N 2 : 217.1705; found: 217.1699
Synthesis of the complex (3) (dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-

1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II)) (Ind II)
Under an argon atmosphere compounds Ind I (3.00 g, 3.25 mmol, 1.0 equiv) and SIMesH(CCl 3 ) (1.66 g, 3.90 mmol,
1.2 equiv) were dissolved in toluene (50 mL). The flask was sealed, placed into pre-heated to 100 °С oil bath and
stirred for 3.5 h. After cooling, the precipitate was filtered off and washed with hexane (15 mL). Filtrate was
evaporated, residue suspended in hexane (10 mL) and cooled to −20 °С. After an hour of cooling the suspension
was filtered and the residue was washed with cooled hexane (−20 °С, 5 mL). Drying the residue in vacuo afforded
(2.54 g, 2.68 mmol, 82.4%) of pure compound (Ind II) as red brown powder. 31P NMR (243 MHz, CDCl 3 ) δ 27.00
(s) ppm.
Preparation of [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](dichloro)[2-(pyrrolidin-1-
ylmethyl)benzylidene]ruthenium (5a)
1 1
4 5
2 2
3 N N 3
1 3 2 1 1
4 4
1 6 6 1
5 5
1 1
Cl
Ru 1
Cl 1 6
2 5
N 2
3 1 1
3 4
4 5
Under an argon atmosphere compound IndII (1.00 g, 1.05 mmol, 1.0 equiv) were dissolved in toluene (12 mL) and
the flask was sealed. The mixture was heated to 90 °C with continuous stirring under an argon atmosphere, then
(4a) (0.37 g, 1.58 mmol, 1.5 equiv) was added in an argon stream. The mixture was heated in a sealed flask at 100 °C
for 3 h. Toluene was evaporated under reduced pressure and the residue was suspended in hexane (10 mL). The
obtained mixture was kept at −20 °C for 10 h. The precipitate was filtered off and washed with hexane (3 × 5 mL)
and then with methanol (3 × 3 mL) to give after drying under vacuum green powder of pure catalyst (5a) (0.54 g,
0.83 mmol, 79%), m.p. 183.2-187.5 °C (decomp.), green prisms after slow crystallization from a heptane-CH 2 Cl 2
mixture.
1Н NMR (300 MHz, CD 2 Cl 2 ) δ 18.84 (s, 1H, CH=Ru), 7.52 (dt, J = 1.0, 7.6 Hz, 1H, H-4-C 6 H 4 ), 7.22 (br. t, J 7.6 Hz, 1H,
H-5-C 6 H 4 ), 7.08 (br. s, 4H, CH-Mes), 6.92 (br. d, J 7.6 Hz, 1H, H-3-C 6 H 4 ), 6.74 (br. d, J 7.6 Hz, 1H, H-6-C 6 H 4 ), 4.26
(s, 2H, N-CH 2 -C 6 H 4 ), 4.11 (s, 4H, N-CH 2 -CH 2 -N), 2,80-2.73 (m, 2H, H-2A,5A-pyrrolidine), 2.53 (s, 12H, Me-ortho-
Mes), 2.46 (s, 6H, Me-para-Mes), 2.17-2.10 (m, 2H, H-2B,5B-pyrrolidine), 1.52-1.43 (m, 2H, H-3A,4A-pyrrolidine),
1.39-1.26 (m, 2H, H-3B,4B-pyrrolidine) ppm.
13C NMR (75 MHz, CD 2 Cl 2 ) δ 312.6 (C=Ru), 212.8 (N-C-N), 149.2 (C-1-C 6 H 4 ), 138.9 (very br. s, 2C, C-1-Mes), 138.4
(2C, C-4-Mes), 136.3 (very br. s, 4C, C-2,6-Mes), 133.9 (C-2-C 6 H 4 ), 130.7 (C-3-C 6 H 4 ), 129.2 (4C, C-3,5-Mes), 128.8 (C-
5-C 6 H 4 ), 128.1 (C-4-C 6 H 4 ), 126.1 (C-6-C 6 H 4 ), 63.2 (N-CH 2 -C 6 H 4 ), 56.4 (2C, C-2,5-pyr), 51.5 (2C, N-CH 2 -CH 2 -N), 23.1
(2C, C-3,4-pyr), 20.8 (2C, Me-4-Mes), 19.3 (br. s, 4C, Me-2,6-Mes) ppm.
IR (KBr): 2948, 2912, 2846, 1604, 1479, 1444, 1415, 1288, 1257, 1182, 1093, 1031, 846, 809, 742, 653, 578 cm–1. HR-MALDI-
ToF MS [M-Сl]+ calcd. for C 33 H 41 ClN 3 Ru: 616.2022; found: 616.2025.
S5
Preparation of [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](dichloro)[2-(piperidin-1-
ylmethyl)benzylidene]ruthenium (5b)
1 1
4 5
2 2
3 N N 3
1 3 2 1 1
4 4
1 6 6 1
5 5
1 1
Cl
Ru 1
Cl 1 6
2 5
3 1N 1 2
6 3 4
4
5
The synthesis method is the same as that of 5a. It did not require further purification and the product was light-
green powder (0.52 g, 0.78 mmol, 74%), m.p. 197.3-200.1 °C (decomp.), green prisms after slow crystallization from
a heptane-CH 2 Cl 2 mixture.
1Н NMR (300.1 MHz, CD 2 Cl 2 ) δ 18.75 (s, 1H, CH=Ru), 7.52 (br. t, J = 7.5 Hz, 1H, H-4-C 6 H 4 ), 7.22 (br. t, J = 7.5 Hz, 1H,
H-5-C 6 H 4 ), 7.10 (br. d, J = 7.5 Hz, 1H, H-3-C 6 H 4 ), 7.08 (br. s, 4H, CH-Mes), 6.73 (br. d, J = 7.5 Hz, 1H, H-6-C 6 H 4 ),
4.47 (s, 2H, N-CH 2 -C 6 H 4 ), 4.11 (s, 4H, N-CH 2 -CH 2 -N), 2,52-2.46 (m, 2H, H-2A,6A-piperidine), 2.52 (br. s, 6H, Me-
ortho-Mes), 2.49 (br. s, 6H, Me-ortho-Mes), 2.44 (s, 6H, Me-para-Mes), 2,32-2.24 (m, 2H, H-2B,6B-piperidine), 1.70-
1.40 (m, 3H, H-3A,4A,5A-piperidine), 1.17-0.94 (m, 3H, H-3B,4B,5B-piperidine) ppm.
(2C, C-4-Mes), 136.6 (very br. s, 4C, C-2,6-Mes), 133.1 (C-2-C 6 H 4 ), 131.1 (C-3-C 6 H 4 ), 129.2 (4C, C-3,5-Mes), 128.5 (C-
5-C 6 H 4 ), 128.3 (C-4-C 6 H 4 ), 125.2 (C-6-C 6 H 4 ), 55.3 (N-CH 2 -C 6 H 4 ), 51.5 (br. s, 2C, N-CH 2 -CH 2 -N), 51.1 (2C, C-2,6-
piperidine), 23.4 (2C, C-3,5-piperidine), 20.8 (2C, Me-4-Mes), 19.7 (C-4-piperidine), 19.1 (very br. s, 4C, Me-2,6-Mes)
ppm.
IR (KBr): 2921, 2854, 1606, 1587, 1481, 1409, 1307, 1253, 1180, 1033, 858, 806, 783, 744, 638, 580 cm–1. HR-MALDI-ToF
MS [M-Сl]+ calcd. for C 34 H 43 ClN 3 Ru: 630.2184; found: 630.2181.
Preparation of [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene] (dichloro)[2-(1,3-dihydro-2H-
isoindol-2-ylmethyl)benzylidene]ruthenium (5c).
1 1
4 5
2 2
3 N N 3
1 2 1
4 4
1 6 6 1
5 5
1 1
Cl
Ru 1
Cl 1 6
1 5
7 7a 2
N 2 A
1
3 4
6 B 3a 3
5 4
green powder (0.55 g, 0.82 mmol, 78%), m.p. 183.2-187.5 °C (decomp.). 1Н NMR (300.1 MHz, CD 2 Cl 2 , 30 °C) δ 18.77
(s, 1H, CH=Ru), 7.52 (dt, J = 1.1, 7.6 Hz, 1H, H-4-C 6 H 4 -A), 7.25 (br. t, J = 7.6 Hz, 1H, H-5-C 6 H 4 -A), 7.20-7.16 (m, 2H,
H-5,6-B), 7.09 (br. s, 4H, CH-Mes), 7.06-7.03 (m, 2H, H-4,7-B), 6.92 (br. d, J = 7.6 Hz, 1H, H-3-C 6 H 4 -A), 6.82 (br. d,
S6
J = 7.6 Hz, 1H, H-6-C 6 H 4 -A), 4.42 (s, 2H, N-CH 2 -C 6 H 4 ), 4.13 (s, 4H, N-CH 2 -CH 2 -N), 3.95 (d, 2H, H-1A,3A), 3.54 (d,
2H, H-1B,3B), 2.51 (br. s, 12H, Me-ortho-Mes), 2.46 (s, 6H, Me-para-Mes) ppm.
13C NMR (75.5 MHz, CD 2 Cl 2 , 30 °C) δ 311.2 (C=Ru), 212.9 (N-C-N), 148.9 (C-1-C 6 H 4 -A), 138.8 (br. s, 2C, C-1-Mes),
138.4 (2C, C-4-Mes), 137.8 (2C, 3a,7a-C 6 H 4 -B), 136.2 (very br. s, 4C, C-2,6-Mes), 133.5 (C-2-C 6 H 4 -A), 131.2 (C-3-C 6 H 4 -
A), 129.2 (4C, C-3,5-Mes), 128.8 (C-5-C 6 H 4 -A), 128.3 (C-4-C 6 H 4 -A), 127.0 (2C, 5,6-C 6 H 4 -B), 126.6 (C-6-C 6 H 4 -A),
122.8 (2C, 4,7-C6H4-B), 61.4 (N-CH 2 -C 6 H 4 -A), 59.9 (2C, C-3,5-C 6 H 4 -B), 51.6 (2C, N-CH 2 -CH 2 -N), 20.8 (2C, Me-4-
Mes), 19.2 (br. s, 4C, Me-2,6-Mes) ppm.
IR (KBr): 2950, 2894, 2852, 1627, 1604, 1481, 1415, 1398, 1255, 1182, 944, 852, 843, 802, 744, 727, 702, 640, 579 cm–1. HR-
MALDI-ToF MS [M-Сl]+ calcd. for C 37 H 41 ClN 3 Ru: 664.2027; found: 664.2023.
Preparation of [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene] (dichloro)[2-(3,4-

dihydroisoquinolin-2(1H)-ylmethyl)benzylidene]ruthenium (5d).
1 1
4 5
2 2
3 N N 3
1 2 1
4 4
1 6 6 1
5 5
1 1
Cl
Ru 1
Cl 1 6
8 1 5
7 8a 2N 1 2 A
B
6 4a 3 3 4
5 4
The synthesis method is the same as that of 5a. It did not require further purification and the product was dark-
green powder (0.52 g, 0.72 mmol, 69%), m.p. 198.8−201.0 °C (decomp.), dark-green plates after slow crystallization
from a heptane-CH 2 Cl 2 mixture.
1Н NMR (300.1 MHz, CD 2 Cl 2 , 30 °C) δ 18.80 (s, 1H, CH=Ru), 7.53 (dt, J = 1.0, 7.5 Hz, 1H, H-4-C 6 H 4 -A), 7.26 (br. d, J
= 7.5 Hz, 1H, H-5-C 6 H 4 -A), 7.14-6.96 (m, 4H, H-Ar, H-5,6,7-B, H-3-A), 7.10 (br. s, 4H, H-Mes), 6.78 (br. d, J = 7.5
Hz, 1H, H-6-A), 6.70 (br. d, J = 7.5 Hz, 1H, H-8-B), 4.52 (br. d, J = 14.1 Hz, 1H, N-CH 2 -C 6 H 4 -endocycl), 4.20 (br. d, J
= 14.1 Hz, 1H, N-CH 2 -C 6 H 4 -endocycl), 4.13 (s, 4H, N-CH 2 -CH 2 -N), 3.62 (d, J = 16.2 Hz, 1H, N-CH 2 -C 6 H 4 -exocycl),
3.22 (d, J = 16.2 Hz, 1H, N-CH 2 -C 6 H 4 -exocycl), 3.02 (ddd, J = 5.2, 10.1, 12.9 Hz, 1H, N-CH 2 -CH 2 -C 6 H 4 -exocycl), 2.68
(m, 3H, N-CH 2 -CH 2 -C 6 H 4 -exocycl), 2.47 (br. s, 12H, Me-ortho-Mes), 2.46 (s, 6H, Me-para-Mes) ppm.
13C NMR (75.5 MHz, CD 2 Cl 2 , 30 °C) δ 312.3 (C=Ru), 212.2 (N-C-N), 148.8 (C-1-C 6 H 4 -A), 139.0 (br. s, 4C, C-3,5-Mes),
138.5 (2C, C-4-Mes), 136.3 (br. s, 2C, C-1-Mes), 132.8 (2C, 4a,8a-C 6 H 4 -B), 132.6 (C-2-C 6 H 4 -A), 131.2 (C-3-C 6 H 4 -A),
129.3 (4C, C-3,5-Mes), 129.0 (C-5-C 6 H 4 -A), 128.3 (C-5-C 6 H 4 -B), 128.2 (C-4-C 6 H 4 -A), 126.5 (2C, 5,6-C 6 H 4 -B), 126.0
(C-6-C 6 H 4 -A), 123.1 (2C, 4,7-C 6 H 4 -B), 57.7 (N-CH 2 -C 6 H 4 -A), 54.9 (N-CH 2 -C 6 H 4 -B), 51.5 (2C, N-CH 2 -CH 2 -N), 49.5
(N-CH 2 -CH 2 -C 6 H 4 -B), 24.0 (N-CH 2 -CH 2 -C 6 H 4 -B), 20.8 (2C, Me-para-Mes), 19.2 (br. s, 4C, Me-ortho-Mes) ppm.
IR (KBr): 2942, 2898, 2856, 1481, 1409, 1263, 1255, 1234, 1182, 1024, 987, 852, 804, 746, 640, 578 cm–1.
HR-MALDI-ToF MS [M-Сl]+ calcd. for C 38 H 43 ClN 3 Ru: 678.2184; found: 678.2180.
Preparation of [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](dichloro) [2-(morpholin-4-
ylmethyl)benzylidene]ruthenium (5e).
S7
1 1
4 5
2 2
3 N N 3
1 2 1
4 4
1 6 6 1
5 5
1 1
Cl
Ru 1
Cl 1 6
2 5
3 1N 1 2
3 4
4O 5 6
The synthesis method is the same as that of 5a. It did not require further purification and the product was green
powder (0.47 g, 0.756 mmol, 72%), m.p. 191.8−193 °C (decomp.), green prisms after slow crystallization from a
hexane-CH 2 Cl 2 mixture.
1Н NMR (300.1 MHz, CD 2 Cl 2 ) δ 18.95 (s, 1H, CH=Ru), 7.49 (br. t, J = 7.4 Hz, 1H, H-4-C 6 H 4 ), 7.25 (br. t, J = 7.4 Hz,
1H, H-5-C 6 H 4 ), 7.10 (s, 4H, H-Mes), 7.07 (br. d, J = 7.4 Hz, 1H, H-3-C 6 H 4 ), 6.66 (br. d, J = 7.4 Hz, 1H, H-6-C 6 H 4 ),
4.12 (br. s, 6H, N-CH 2 -CH 2 -N and N-CH 2 -C 6 H 4 ), 3.56 (ddd, 2H, J = 2.2, 7.0, 12.3 Hz, H-2,6-Morph), 3.24-3.18 (m,
2H, H-2,6-Morph), 3.10-3.03 (m, 2H, H-3,5-Morph), 2.53 (br. s, 12H, Me-ortho-Mes), 2.44 (s, 6H, Me-para-Mes), 2.04
(ddd, 2H, J = 2.0, 5.9, 12.3 Hz, H-3,5-Morph) ppm.
13C NMR (75 MHz, CD 2 Cl 2 ) δ 316.2 (C=Ru), 210.7 (N-C-N), 151.3 (C-2-C 6 H 4 ), 139.2 (very br. s, 4C, C-2,6-Mes), 138.7
(2C, C-4-Mes), 136.2 (br. s, 2C, C-4-Mes), 131.5 (C-3-C 6 H 4 ), 130.8 (C-1-C 6 H 4 ), 129.3 (4C, C-3,5-Mes), 129.1 (C-5-C6H4),
128.1 (C-4-C 6 H 4 ), 122.2 (C-6-C 6 H 4 ), 62.7 (2C, C-2,6-Morpholine), 60.6 (N-CH 2 -C 6 H 4 ), 53.1 (2C, C-3,5-Morpholine),
51.6 (2C, N-CH 2 -CH 2 -N), 20.8 (2C, Me-4-Mes), ~ 19.4 (very br. s, 4C, Me-2,6-Mes) ppm.
IR (KBr): 2953, 2914, 1934, 1607, 1483, 1449, 1397, 1258, 1112, 996, 871, 852, 785, 749, 731, 580 cm–1.
HR-MALDI-ToF MS [M-Сl]+ calcd. for C 33 H 41 ClN 3 ORu: 632.1976; found: 632.1973.
Preparation of [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](dichloro){2-[(4-methylpiperazin-1-
yl)methyl]benzylidene}ruthenium (5f)
1 1
4 5
2 2
3 N N 3
1 2 1
4 4
1 6 6 1
5 5
1 1
Cl
Ru 1
Cl 1 6
2 5
3 1N 1 2
6 3 4
N
Me 4 5
1
green (0.57 g, 0.75 mmol, 71%), m.p. 206.3−209.0 °C (decomp.), green prisms after slow crystallization from a
heptane-CH 2 Cl 2 mixture.
1Н NMR (300.1 MHz, CD 2 Cl 2 ) δ 18.79 (s, 1H, CH=Ru), 7.52 (br. t, J = 7.6 Hz, 1H, H-4-C 6 H 4 ), 7.23 (br. t, J = 7.6 Hz,
1H, H-5-C 6 H 4 ), 7.08 (s, 4H, H-Mes) 7.06 (br.d, J = 7.6 Hz, 1H, H-3-C 6 H 4 ), 6.72 (br. d, J = 7.6 Hz, 1H, H-6-C 6 H 4 ),
4.35 (br. s, 2H, N-CH 2 -C 6 H 4 ), 4.11 (s, 4H, N-CH 2 -CH 2 -N), 2.86-2.79 (m, 2H, H-2,6-piperazine-A), 2.51 (br. s, 12H),
2,46-2.20 (m, 6H, H-2,6-piperazine-B and H-3,5-piperazine), 2.43 (s, 6H, Me-ortho-Mes), 2.14 (s, 3H, N-Me) ppm.
S8
(4C, C-2,6-Mes), 132.2 (C-2-C 6 H 4 ), 131.3 (C-3-C 6 H 4 ), 129.3 (4C, C-3,5-Mes), 128.8 (C-5-C 6 H 4 ), 128.2 (C-4-C 6 H 4 ), 124.8
(C-6-C 6 H 4 ), 56.8 (N-CH 2 -C 6 H 4 ), 51.4 (br. s, 2C, N-CH 2 -CH 2 -N), 51.0 (2C, C-2,6-piperazine), 49.4 (2C, C-3,5-
piperazine), 45.6 (Me-N), 20.8 (2C, Me-4-Mes), 19.25 (very br. s, 4C, Me-2,6-Mes) ppm.
IR (KBr): 3010, 2954, 2917, 2838, 2782, 1606, 1479, 1440, 1413, 1286, 1257, 1147, 1043, 1007, 964, 852, 802, 777, 740, 638,
579 cm–1.
HR-MALDI-ToF MS [M-Сl]+ calcd. for C 34 H 44 ClN 4 Ru: 645.2293, found: 645.2283.
Procedure for the self-cross-metathesis reaction.

Each metathesis experiment was carried out 3 times; the ratios of the components of the reaction mixtures
were averaged.
Styrene (6) (0.51 g, 4.80 mmol), was added to a 0.10 mol % solution of catalyst (5a−f) in dry solvent (10 mL)
in a Schlenk flask purged with argon. The resulting mixture was stirred at r.t. or heated at reflux for 1 h (see Table
4) under an argon atmosphere. Catalyst was separated by filtration of the reaction mixture through basic Al 2 O 3 (1.5
× 2 cm), CH 2 Cl 2 (2 × 10 mL) was used as an eluent. Solvent was gently evaporated under atmospheric pressure to
give a mixture of starting material (6) and stilbene (7). Compositions of these mixtures were established using 1H
NMR analysis.
Procedure for the RCM reaction.
Diallyltosylamide (8) (0.50 g, 2.0 mmol) was added to a 0.1 mol % or 0.01 mol% solution of catalyst (5a−f)
(see Table 5) in dry chloroform (10 mL) in a Schlenk flask purged with argon. The resulting mixture was kept at r.t.
under continuous stirring in an argon atmosphere for 1 h. Catalyst was separated by filtration of the reaction
mixture through basic Al 2 O 3 (1.5 × 2 cm), CH 2 Cl 2 (2 × 10 mL) was used as an eluent. Solvent was evaporated under
reduced pressure to give a mixture of 8 and metathesis product 1-tosyl-2,5-dihydro-1H-pyrrole (9). Compositions
of these mixtures were established using 1H NMR analysis.
Procedure for the cross-metathesis reaction.

Styrene (6) (0.31 g, 3.00 mmol) and (Z)-1,4-diacetoxy-2-butene (10) (0.25 g, 1.5 mmol) were dissolved in dry
CH 2 Cl 2 (9 mL) then a 0.10 mol % solution of catalyst (5a−f) in dry CH 2 Cl 2 (1 mL) was added and reaction flask was
purged with argon. The resulting mixture was stirred at 120 ℃ under microwave irradiation (200 W) for 15 min.
Catalyst was separated by filtration of the reaction mixture through basic Al 2 O 3 (1.5 × 2 cm), CH 2 Cl 2 (2 × 10 mL)
was used as an eluent. Solvent was gently evaporated under reduced pressure to give a mixture of starting material
(with the exception of styrene) and products. Yields and compositions of these mixtures were established using 1H
NMR analysis (see Table 6 of the main part).
Experimental part for X-ray analysis
The single-crystal X-ray diffraction data for compounds 5a−f were collected at 100 K on a Bruker Kappa Apex
II automatic four-circle diffractometer equipped with an area detector (Mo-Kα sealed-tube X-ray source, λ = 0.71073
Å, graphite monochromator).
The unit cell parameters were refined over the whole dataset [1]. The experimental reflection intensities
were corrected for absorption using SADABS program [2]. The structures were solved by direct method using
S9
SHELXS and refined by full-matrix least-squares on F2 using SHELXL software [3] in the anisotropic approximation
for all nonhydrogen atoms. The hydrogen atoms were placed in the geometrically calculated positions with the
isotropic temperature factors set at 1.2 times (CH groups) or 1.5 times (CH 3 group) the equivalent isotropic
temperature factor of their bonded C atoms. Tables and pictures for structures were generated using Olex2 [4] as
GUI. In structure 5b solvent molecule was strongly disordered and therefore it was removed using the SQUEEZE
routine of PLATON [5], and the structure was then refined again using the data generated. The final composition
reported in 5b cif-file contains one CH 2 Cl 2 molecule for one complex molecule. Table S1 lists the crystallographic
characteristics and details of the diffraction experiment. All other crystallographic parameters of molecules 5a−f
are shown in Figures S1−S6 and indicated in Tables S2−S20.
X-ray diffraction experiments were performed at the Center for Shared Use of Physical Methods of
Investigation at the Frumkin Institute of Physical Chemistry and Electrochemistry, RAS.
Atomic coordinates for 5a−f have been deposited with the Cambridge Crystallographic Data Centre,
CCDC numbers are 1957385−1957390. The supplementary crystallographic data can be obtained free of charge from
the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
S10
Table S1. Crystal data and structure refinement for complexes 5a−f.
Compound 5a 5b* 5c 5d 5e 5f
CCDC number 1957386 1957387 1957389 1957388 1957390 1957385
Empirical formula C 34 H 43 Cl 4 N 3 Ru C 35 H 45 Cl 4 N 3 Ru C 37 H 41 Cl 2 N 3 Ru C 38 H 43 Cl 2 N 3 Ru C 33 H 41 Cl 2 N 3 ORu C 34 H 44 Cl 2 N 4 Ru
Formula weight 736.58 750.61 699.70 713.72 667.66 680.70
Temperature/K 100(2) 100(2) 100(2) 100(2) 100(2) 100(2)
Crystal system monoclinic monoclinic monoclinic triclinic monoclinic monoclinic
Space group P2 1 /n P2 1 /n P2 1 /n P-1 P2 1 /c P2 1 /n
a/Å 13.8908(6) 13.7150(4) 10.6183(3) 9.2706(2) 23.1097(5) 10.3753(6)
b/Å 10.1857(4) 10.6439(3) 25.2739(6) 10.5001(3) 17.8183(4) 25.3854(19)
c/Å 23.9486(9) 23.9739(6) 12.5593(3) 18.6013(5) 23.1003(5) 12.4498(8)
α/° 90 90 90 93.910(1) 90 90
β/° 93.355(1) 93.652(1) 105.925(1) 96.084(1) 103.2580(10) 107.615(3)
γ/° 90 90 90 111.245(1) 90 90
Volume/Å3 3382.6(2) 3492.63(17) 3241.13(14) 1666.99(8) 9258.6(4) 3125.3(4)
Z 4 4 4 2 12 4
ρ calc g/cm3 1.446 1.427 1.434 1.422 1.437 1.447
μ/mm-1 0.807 0.784 0.680 0.662 0.712 0.703
F(000) 1520.0 1552.0 1448.0 740.0 4152.0 1416.0
Crystal size/mm3 0.440 × 0.320 × 0.180 0.400 × 0.380 × 0.200 0.400 × 0.320 × 0.260 0.400 × 0.220 × 0.180 0.360 × 0.320 × 0.150 0.200 × 0.160 × 0.060
Radiation MoKα (λ = 0.71073) MoKα (λ = 0.71073) MoKα (λ = 0.71073) MoKα (λ = 0.71073) MoKα (λ = 0.71073) MoKα (λ = 0.71073)
2Θ range for data collection/° 8.182 to 59.998 8.208 to 59.998 8.304 to 69.998 8.176 to 69.998 8.154 to 60 7.572 to 54.994
Index ranges -19 ≤ h ≤ 19, -14 ≤ k ≤ 14, -19 ≤ h ≤ 19, -14 ≤ k ≤ 14, -17 ≤ h ≤ 17, -40 ≤ k ≤ -14 ≤ h ≤ 14, -16 ≤ k ≤ 16, -32 ≤ h ≤ 26, -25 ≤ k ≤ -13 ≤ h ≤ 12, -30 ≤ k ≤
-33 ≤ l ≤ 18 -33 ≤ l ≤ 33 40, -18 ≤ l ≤ 20 -28 ≤ l ≤ 30 25, -32 ≤ l ≤ 30 32, -16 ≤ l ≤ 16
Reflections collected 32183 36281 93128 52409 114769 32187
Independent reflections 9842 [R int = 0.0318, 9857 [R int = 0.0317, 14249 [R int = 0.0404, 14623 [R int = 0.0277, 26888 [R int = 0.0846, 7151 [R int = 0.1430, R sigma
R sigma = 0.0324] R sigma = 0.0323] R sigma = 0.0263] R sigma = 0.0279] R sigma = 0.0854] = 0.1491]
Data/restraints/parameters 9842/0/385 9857/0/367 14249/0/398 14623/0/403 26888/0/1099 7151/0/377
Goodness-of-fit on F2 1.031 1.036 1.051 1.037 0.995 0.975
Final R indexes [I>=2σ (I)] R 1 = 0.0302, wR 2 = R 1 = 0.0313, wR 2 = R 1 = 0.0268, wR 2 = R 1 = 0.0255, wR 2 = R 1 = 0.0434, wR 2 = R 1 = 0.0553, wR 2 =
0.0675 0.0720 0.0624 0.0622 0.0773 0.0880
Final R indexes [all data] R 1 = 0.0383, wR 2 = R 1 = 0.0442, wR 2 = R 1 = 0.0338, wR 2 = R 1 = 0.0312, wR 2 = R 1 = 0.0918, wR 2 = R 1 = 0.1290, wR 2 =
0.0715 0.0790 0.0656 0.0649 0.0923 0.1096
Largest diff. peak/hole / e Å-3 1.29/-1.23 0.77/-0.54 0.64/-0.53 0.83/-0.65 0.94/-0.78 0.67/-0.83
* After SQUEEZE procedure. The final composition contains one squeezed CH 2 Cl 2 molecule for one complex molecule.
S11
Table S2. Selected bond distances (Å) and angles (°) for 5a−f.
Compound 5a 5b 5c 5d 5e* 5f
Ru(1)─C(38) 1.8316(17) 1.826(2) 1.8294(11) 1.8325(11) 1.820(3) – 1.831(3) 1.815(4)
Ru(1)─C(2) 2.0431(17) 2.0352(18) 2.0370(10) 2.0303(10) 2.015(3) – 2.027(3) 2.027(5)
Ru(1)─N(2) 2.2233(15) 2.2428(15) 2.2274(9) 2.2969(9) 2.323(2) – 2.340(2) 2.251(4)
Ru(1)─Cl(1) 2.3511(4) 2.3668(5) 2.3516(3) 2.3632(3) 2.3582(7) –2.3668(7) 2.3517(13)
Ru(1)─Cl(2) 2.3602(4) 2.3562(5) 2.3545(3) 2.3594(3) 2.3704(7) –2.3820(7) 2.3537(12)
N(2)─C(41) 1.505(2) 1.492(3) 1.5045(14) 1.5045(14) 1.483(3) – 1.494(3) 1.492(5)
N(2)─C(45) 1.523(2) 1.494(2) 1.5092(14) 1.5092(14) 1.483(3) – 1.496(3) 1.493(5)
N(2)─C(37) 1.488(2) 1.486(2) 1.4931(14) 1.4931(14) 1.478(4) – 1.488(4) 1.496(5)
C(32)─C(37) 1.500(2) 1.495(3) 1.4991(17) 1.4991(17) 1.499(4) – 1.501(4) 1.491(6)
C(31)─C(32) 1.416(2) 1.418(3) 1.4129(16) 1.4129(16) 1.398(4) – 1.405(4) 1.404(6)
C(31)─C(38) 1.467(2) 1.457(3) 1.4610(15) 1.4610(15) 1.460(3) – 1.471(3) 1.468(6)
N(1)─C(2) 1.351(2) 1.346(3) 1.3493(13) 1.3493(13) 1.331(3) – 1.341(3) 1.347(5)
N(1)─C(5) 1.478(2) 1.479(2) 1.4768(15) 1.4768(15) 1.479(3) – 1.485(3) 1.473(6)
N(3)─C(2) 1.357(2) 1.351(3) 1.3569(14) 1.3569(14) 1.351(3) – 1.353(3) 1.360(5)
N(3)─C(4) 1.474(2) 1.478(2) 1.4733(14) 1.4733(14) 1.473(3) – 1.477(3) 1.472(6)

S12
C(4)─C(5) 1.518(3) 1.510(3) 1.5157(18) 1.5157(18) 1.511(4) – 1.529(4) 1.515(6)
C(38)─Ru(1)─C(2) 99.60(7) 100.90(8) 98.72(4) 98.72(4) 98.64(12) – 99.06(12) 99.31(19)
C(38)─Ru(1)─N(2) 88.35(6) 89.72(7) 88.22(4) 88.22(4) 92.01(10) – 93.14(10) 87.69(17)
C(2)─Ru(1)─N(2) 170.93(6) 168.80(7) 172.67(4) 172.67(4) 167.79(10) – 169.00(10) 172.84(16)
C(38)─Ru(1)─C1(1) 100.00(5) 97.21(6) 101.55(4) 101.55(4) 95.35(8) – 97.20(9) 98.58(15)
C(2)─Ru(1)─C1(1) 84.74(5) 85.44(5) 88.81(3) 88.81(3) 91.10(7) – 92.22(7) 88.11(13)
N(2)─Ru(1)─C1(1) 89.61(4) 89.72(4) 87.48(2) 87.48(2) 87.14(5) – 87.92(6) 89.38(10)
C(38)─Ru(1)─C1(2) 101.99(5) 99.38(6) 99.98(4) 99.98(4) 92.51(9) – 92.76(8) 100.49(15)
C(2)─Ru(1)─C1(2) 95.43(5) 92.58(5) 90.15(3) 90.15(3) 86.22(7) – 87.52(7) 89.45(13)
N(2)─Ru(1)─C1(2) 87.11(4) 89.16(4) 90.97(2) 90.97(2) 91.50(6) – 92.54(6) 90.75(10)
C1(1)─Ru(1)─C1(2) 157.658(17) 163.364(19) 158.354(11) 158.354(11) 170.25(3) – 172.03(3) 160.92(4)
C(37)─N(2)─Ru(1) 109.21(10) 108.02(11) 111.04(6) 111.04(6) 106.86(17) – 107.64(17) 108.8(3)
C(31)─C(38)─Ru(1) 128.74(13) 128.94(14) 130.39(8) 130.39(8) 122.9(2) – 123.7(2) 129.5(3)
N(1)─C(2)─Ru(1) 132.21(12) 132.92(15) 131.95(8) 131.95(8) 134.5(2) – 135.6(2) 131.3(3)
N(3)─C(2)─Ru(1) 120.24(12) 119.33(14) 121.09(7) 121.09(7) 117.1(2) – 117.4(2) 122.2(3)
* The range of values for the three crystallographically independent molecules is given.
13
Figure S1. Solid-state crystal structure of compound 5a
Table S3. Bond lengths for 5a.

Atom Atom Length (Å) Atom Atom Length (Å)
Ru(1) C(38) 1.8316(17) C(14) C(18) 1.510(3)
Ru(1) C(2) 2.0431(17) C(15) C(16) 1.401(3)
Ru(1) N(2) 2.2233(15) C(16) C(19) 1.504(3)
Ru(1) Cl(1) 2.3511(4) C(21) C(26) 1.397(2)
Ru(1) Cl(2) 2.3602(4) C(21) C(22) 1.403(2)
Cl(3) C(1) 1.750(3) C(22) C(23) 1.395(3)
Cl(4) C(1) 1.766(3) C(22) C(27) 1.509(2)
N(1) C(2) 1.351(2) C(23) C(24) 1.398(3)
N(1) C(21) 1.435(2) C(24) C(25) 1.385(3)
N(1) C(5) 1.478(2) C(24) C(28) 1.509(3)
N(2) C(37) 1.488(2) C(25) C(26) 1.397(3)
N(2) C(41) 1.505(2) C(26) C(29) 1.508(3)
N(2) C(45) 1.523(2) C(31) C(36) 1.407(2)
N(3) C(2) 1.357(2) C(31) C(32) 1.416(2)
N(3) C(11) 1.438(2) C(31) C(38) 1.467(2)
N(3) C(4) 1.474(2) C(32) C(33) 1.395(2)
C(4) C(5) 1.518(3) C(32) C(37) 1.500(2)
C(11) C(16) 1.401(2) C(33) C(34) 1.388(3)
C(11) C(12) 1.408(3) C(34) C(35) 1.388(3)
C(12) C(13) 1.391(3) C(35) C(36) 1.390(3)
C(12) C(17) 1.507(3) C(41) C(43) 1.524(3)
C(13) C(14) 1.392(3) C(43) C(44) 1.535(3)
C(14) C(15) 1.383(3) C(44) C(45) 1.526(2)
Table S4. Bond angles for 5a.

Atom Atom Atom Angle (°) Atom Atom Atom Angle (°)
C(38) Ru(1) C(2) 99.60(7) C(15) C(14) C(18) 121.2(2)
14
C(38) Ru(1) N(2) 88.35(6) C(13) C(14) C(18) 120.3(2)

C(2) Ru(1) N(2) 170.93(6) C(14) C(15) C(16) 122.15(19)
C(38) Ru(1) Cl(1) 100.00(5) C(11) C(16) C(15) 117.68(18)
C(2) Ru(1) Cl(1) 84.74(5) C(11) C(16) C(19) 123.09(16)
N(2) Ru(1) Cl(1) 89.61(4) C(15) C(16) C(19) 119.21(17)
C(38) Ru(1) Cl(2) 101.99(5) C(26) C(21) C(22) 121.67(16)
C(2) Ru(1) Cl(2) 95.43(5) C(26) C(21) N(1) 119.14(16)
N(2) Ru(1) Cl(2) 87.11(4) C(22) C(21) N(1) 118.97(15)
Cl(1) Ru(1) Cl(2) 157.658(17) C(23) C(22) C(21) 118.24(16)
C(2) N(1) C(21) 128.51(14) C(23) C(22) C(27) 120.91(17)
C(2) N(1) C(5) 113.79(14) C(21) C(22) C(27) 120.85(16)
C(21) N(1) C(5) 116.76(14) C(22) C(23) C(24) 121.54(18)
C(37) N(2) C(41) 108.87(14) C(25) C(24) C(23) 118.37(17)
C(37) N(2) C(45) 107.88(14) C(25) C(24) C(28) 120.63(19)
C(41) N(2) C(45) 105.25(13) C(23) C(24) C(28) 120.97(19)
C(37) N(2) Ru(1) 109.21(10) C(24) C(25) C(26) 122.30(17)
C(41) N(2) Ru(1) 106.65(11) C(25) C(26) C(21) 117.82(17)
C(45) N(2) Ru(1) 118.61(10) C(25) C(26) C(29) 120.60(17)
C(2) N(3) C(11) 126.06(15) C(21) C(26) C(29) 121.57(17)
C(2) N(3) C(4) 114.11(14) C(36) C(31) C(32) 118.06(16)
C(11) N(3) C(4) 119.17(14) C(36) C(31) C(38) 117.36(16)
Cl(3) C(1) Cl(4) 110.28(15) C(32) C(31) C(38) 124.56(16)
N(1) C(2) N(3) 106.35(14) C(33) C(32) C(31) 119.45(17)
N(1) C(2) Ru(1) 132.21(12) C(33) C(32) C(37) 117.64(16)
N(3) C(2) Ru(1) 120.24(12) C(31) C(32) C(37) 122.89(15)
N(3) C(4) C(5) 102.33(14) C(34) C(33) C(32) 121.53(18)
N(1) C(5) C(4) 102.73(14) C(33) C(34) C(35) 119.55(18)
C(16) C(11) C(12) 121.55(16) C(34) C(35) C(36) 119.79(18)
C(16) C(11) N(3) 120.42(16) C(35) C(36) C(31) 121.60(17)
C(12) C(11) N(3) 117.75(16) N(2) C(37) C(32) 112.06(14)
C(13) C(12) C(11) 117.88(18) C(31) C(38) Ru(1) 128.74(13)
C(13) C(12) C(17) 120.47(17) N(2) C(41) C(43) 105.63(15)
C(11) C(12) C(17) 121.62(17) C(41) C(43) C(44) 100.76(15)
C(12) C(13) C(14) 122.08(18) C(45) C(44) C(43) 102.54(15)
C(15) C(14) C(13) 118.51(18) N(2) C(45) C(44) 106.55(14)
Table S5. Hydrogen bonds for 5a.

D H A d(D-H) (Å) d(H-A) (Å) d(D-A) (Å) D-H-A (°)
C(5) H(5A) Cl(2) 1 0.99 2.77 3.6347(19) 146.0
C(37) H(37A) Cl(1)2 0.99 2.68 3.5917(17) 152.4
C(37) H(37B) Cl(1) 0.99 2.49 3.1904(19) 127.7
C(45) H(45B) Cl(2) 0.99 2.56 3.1675(19) 119.2
11/2-X,1/2+Y,3/2-Z; 23/2-X,-1/2+Y,3/2-Z
15
Figure S2. Solid-state crystal structure of compound 5b
Table S6. Bond lengths for 5b.

Ru(1) C(38) 1.826(2) C(16) C(19) 1.493(3)
Ru(1) C(2) 2.0352(18) C(21) C(26) 1.396(3)
Ru(1) N(2) 2.2428(15) C(21) C(22) 1.401(3)
Ru(1) Cl(2) 2.3562(5) C(22) C(23) 1.387(4)
Ru(1) Cl(1) 2.3668(5) C(22) C(27) 1.506(3)
N(1) C(2) 1.346(3) C(23) C(24) 1.396(4)
N(1) C(21) 1.430(3) C(24) C(25) 1.388(3)
N(1) C(5) 1.479(2) C(24) C(28) 1.507(4)
N(2) C(37) 1.486(2) C(25) C(26) 1.388(3)
N(2) C(41) 1.492(3) C(26) C(29) 1.505(3)
N(2) C(45) 1.494(2) C(31) C(36) 1.403(3)
N(3) C(2) 1.351(3) C(31) C(32) 1.418(3)
N(3) C(11) 1.439(3) C(31) C(38) 1.457(3)
N(3) C(4) 1.478(2) C(32) C(33) 1.398(3)
C(4) C(5) 1.510(3) C(32) C(37) 1.495(3)
C(11) C(16) 1.396(3) C(33) C(34) 1.384(3)
C(11) C(12) 1.398(3) C(34) C(35) 1.382(3)
C(12) C(13) 1.393(4) C(35) C(36) 1.384(3)
C(12) C(17) 1.497(4) C(41) C(42) 1.526(3)
C(13) C(14) 1.383(5) C(42) C(43) 1.515(4)
C(14) C(15) 1.376(4) C(43) C(44) 1.514(4)
C(14) C(18) 1.526(5) C(44) C(45) 1.530(3)
C(15) C(16) 1.394(4)
Table S7. Bond angles for 5b.

C(38) Ru(1) C(2) 100.90(8) C(13) C(14) C(18) 120.4(3)
C(38) Ru(1) N(2) 89.72(7) C(14) C(15) C(16) 122.0(3)
C(2) Ru(1) N(2) 168.80(7) C(15) C(16) C(11) 118.1(2)
16
C(38) Ru(1) Cl(2) 99.38(6) C(15) C(16) C(19) 118.6(2)

C(2) Ru(1) Cl(2) 92.58(5) C(11) C(16) C(19) 123.2(2)
N(2) Ru(1) Cl(2) 89.16(4) C(26) C(21) C(22) 121.5(2)
C(38) Ru(1) Cl(1) 97.21(6) C(26) C(21) N(1) 119.68(18)
C(2) Ru(1) Cl(1) 85.44(5) C(22) C(21) N(1) 118.74(19)
N(2) Ru(1) Cl(1) 89.72(4) C(23) C(22) C(21) 117.8(2)
Cl(2) Ru(1) Cl(1) 163.364(19) C(23) C(22) C(27) 121.2(2)
C(2) N(1) C(21) 127.08(17) C(21) C(22) C(27) 121.0(2)
C(2) N(1) C(5) 113.42(18) C(22) C(23) C(24) 122.4(2)
C(21) N(1) C(5) 118.53(17) C(25) C(24) C(23) 117.8(2)
C(37) N(2) C(41) 110.16(14) C(25) C(24) C(28) 120.0(3)
C(37) N(2) C(45) 109.80(15) C(23) C(24) C(28) 122.2(2)
C(41) N(2) C(45) 108.38(17) C(24) C(25) C(26) 122.1(2)
C(37) N(2) Ru(1) 108.02(11) C(25) C(26) C(21) 118.3(2)
C(41) N(2) Ru(1) 102.91(11) C(25) C(26) C(29) 120.4(2)
C(45) N(2) Ru(1) 117.29(11) C(21) C(26) C(29) 121.3(2)
C(2) N(3) C(11) 126.20(16) C(36) C(31) C(32) 118.16(18)
C(2) N(3) C(4) 113.47(17) C(36) C(31) C(38) 117.47(17)
C(11) N(3) C(4) 119.72(17) C(32) C(31) C(38) 124.37(18)
N(1) C(2) N(3) 107.03(16) C(33) C(32) C(31) 118.86(19)
N(1) C(2) Ru(1) 132.92(15) C(33) C(32) C(37) 118.17(17)
N(3) C(2) Ru(1) 119.33(14) C(31) C(32) C(37) 122.96(17)
N(3) C(4) C(5) 102.58(17) C(34) C(33) C(32) 121.5(2)
N(1) C(5) C(4) 102.75(16) C(35) C(34) C(33) 120.0(2)
C(16) C(11) C(12) 121.4(2) C(34) C(35) C(36) 119.5(2)
C(16) C(11) N(3) 120.55(19) C(35) C(36) C(31) 122.0(2)
C(12) C(11) N(3) 117.9(2) N(2) C(37) C(32) 112.53(15)
C(13) C(12) C(11) 117.5(3) C(31) C(38) Ru(1) 128.94(14)
C(13) C(12) C(17) 120.6(2) N(2) C(41) C(42) 114.51(18)
C(11) C(12) C(17) 121.9(2) C(43) C(42) C(41) 110.40(19)
C(14) C(13) C(12) 122.6(3) C(44) C(43) C(42) 111.4(2)
C(15) C(14) C(13) 118.2(3) C(43) C(44) C(45) 110.8(2)
C(15) C(14) C(18) 121.3(4) N(2) C(45) C(44) 113.13(17)
Table S8. Hydrogen bonds for 5b.

C(5) H(5A) Cl(2) 1 0.99 2.81 3.629(2) 140.3
C(37) H(37A) Cl(1)2 0.99 2.81 3.7441(18) 156.8
C(37) H(37B) Cl(1) 0.99 2.48 3.1965(19) 128.9
C(41) H(41B) Cl(1) 0.99 2.80 3.459(2) 124.8
C(45) H(45B) Cl(2) 0.99 2.54 3.169(2) 121.4
11/2-X,1/2+Y,3/2-Z; 23/2-X,-1/2+Y,3/2-Z
17
Figure S3. Solid-state crystal structure of compound 5c
Table S9. Bond lengths for 5c.

Ru(1) Cl(1) 2.3516(3) C(21) C(26) 1.4005(16)
Ru(1) Cl(2) 2.3545(3) C(22) C(23) 1.3953(17)
Ru(1) N(2) 2.2274(9) C(22) C(27) 1.5013(17)
Ru(1) C(2) 2.0370(10) C(23) C(24) 1.3894(19)
Ru(1) C(38) 1.8294(11) C(24) C(25) 1.3925(19)
N(1) C(2) 1.3493(13) C(24) C(28) 1.5075(19)
N(1) C(5) 1.4768(15) C(25) C(26) 1.3956(17)
N(1) C(21) 1.4292(15) C(26) C(29) 1.5062(17)
N(2) C(37) 1.4931(14) C(31) C(32) 1.4129(16)
N(2) C(41) 1.5045(14) C(31) C(36) 1.4066(16)
N(2) C(45) 1.5092(14) C(31) C(38) 1.4610(15)
N(3) C(2) 1.3569(14) C(32) C(33) 1.3965(17)
N(3) C(4) 1.4733(14) C(32) C(37) 1.4991(17)
N(3) C(11) 1.4339(14) C(33) C(34) 1.393(2)
C(4) C(5) 1.5157(18) C(34) C(35) 1.381(2)
C(11) C(12) 1.4052(16) C(35) C(36) 1.3877(18)
C(11) C(16) 1.4033(16) C(41) C(43) 1.5106(15)
C(12) C(13) 1.3938(17) C(43) C(44) 1.3896(16)
C(12) C(17) 1.5062(17) C(43) C(46) 1.3864(16)
C(13) C(14) 1.3950(18) C(44) C(45) 1.5022(15)
C(14) C(15) 1.3868(17) C(44) C(49) 1.3860(15)
C(14) C(18) 1.5088(17) C(46) C(47) 1.3948(18)
C(15) C(16) 1.4024(16) C(47) C(48) 1.391(2)
C(16) C(19) 1.5058(18) C(48) C(49) 1.3973(18)
C(21) C(22) 1.3991(16)
18
Table S10. Bond angles for 5c.

Cl(1) Ru(1) Cl(2) 158.354(11) C(15) C(16) C(19) 118.85(11)
N(2) Ru(1) Cl(1) 87.48(2) C(22) C(21) N(1) 119.11(10)
N(2) Ru(1) Cl(2) 90.97(2) C(22) C(21) C(26) 121.45(10)
C(2) Ru(1) Cl(1) 88.81(3) C(26) C(21) N(1) 119.36(10)
C(2) Ru(1) Cl(2) 90.15(3) C(21) C(22) C(27) 121.30(11)
C(2) Ru(1) N(2) 172.67(4) C(23) C(22) C(21) 118.41(11)
C(38) Ru(1) Cl(1) 101.55(4) C(23) C(22) C(27) 120.28(11)
C(38) Ru(1) Cl(2) 99.98(4) C(24) C(23) C(22) 121.63(12)
C(38) Ru(1) N(2) 88.22(4) C(23) C(24) C(25) 118.58(11)
C(38) Ru(1) C(2) 98.72(4) C(23) C(24) C(28) 120.44(13)
C(2) N(1) C(5) 113.73(9) C(25) C(24) C(28) 120.98(13)
C(2) N(1) C(21) 128.55(9) C(24) C(25) C(26) 121.85(12)
C(21) N(1) C(5) 117.38(9) C(21) C(26) C(29) 120.99(11)
C(37) N(2) Ru(1) 111.04(6) C(25) C(26) C(21) 118.07(11)
C(37) N(2) C(41) 107.23(8) C(25) C(26) C(29) 120.90(11)
C(37) N(2) C(45) 108.56(8) C(32) C(31) C(38) 125.03(10)
C(41) N(2) Ru(1) 108.39(6) C(36) C(31) C(32) 118.59(10)
C(41) N(2) C(45) 103.49(8) C(36) C(31) C(38) 116.36(10)
C(45) N(2) Ru(1) 117.45(6) C(31) C(32) C(37) 121.93(10)
C(2) N(3) C(4) 113.56(9) C(33) C(32) C(31) 118.93(11)
C(2) N(3) C(11) 127.15(9) C(33) C(32) C(37) 119.14(11)
C(11) N(3) C(4) 118.87(9) C(34) C(33) C(32) 121.63(13)
N(1) C(2) Ru(1) 131.95(8) C(35) C(34) C(33) 119.44(12)
N(1) C(2) N(3) 106.63(9) C(34) C(35) C(36) 120.09(12)
N(3) C(2) Ru(1) 121.09(7) C(35) C(36) C(31) 121.30(12)
N(3) C(4) C(5) 102.68(9) N(2) C(37) C(32) 112.27(9)
N(1) C(5) C(4) 102.48(9) C(31) C(38) Ru(1) 130.39(8)
C(12) C(11) N(3) 117.94(10) N(2) C(41) C(43) 103.82(9)
C(16) C(11) N(3) 120.98(10) C(44) C(43) C(41) 108.60(9)
C(16) C(11) C(12) 120.95(10) C(46) C(43) C(41) 130.83(11)
C(11) C(12) C(17) 121.79(11) C(46) C(43) C(44) 120.57(11)
C(13) C(12) C(11) 118.52(11) C(43) C(44) C(45) 109.20(9)
C(13) C(12) C(17) 119.69(11) C(49) C(44) C(43) 121.17(10)
C(12) C(13) C(14) 122.03(11) C(49) C(44) C(45) 129.63(11)
C(13) C(14) C(18) 121.24(12) C(44) C(45) N(2) 104.24(8)
C(15) C(14) C(13) 117.99(11) C(43) C(46) C(47) 118.50(12)
C(15) C(14) C(18) 120.71(12) C(48) C(47) C(46) 120.98(11)
C(14) C(15) C(16) 122.37(11) C(47) C(48) C(49) 120.22(11)
C(11) C(16) C(19) 123.05(10) C(44) C(49) C(48) 118.50(12)
C(15) C(16) C(11) 117.95(11)
Table S11. Hydrogen bonds for 5c.

C(5) H(5A) Cl(2) 1 0.99 2.92 3.8917(14) 167.6
C(37) H(37B) Cl(1) 0.99 2.57 3.2483(12) 125.3
C(41) H(41B) Cl(1)2 0.99 2.72 3.6502(11) 157.4
C(45) H(45A) Cl(2) 0.99 2.47 3.2133(11) 132.0
1-1/2+X,3/2-Y,-1/2+Z; 21-X,2-Y,2-Z
19
Figure S4. Solid-state crystal structure of compound 5d
Table S12. Bond lengths for 5d.

Ru(1) Cl(1) 2.3632(3) C(21) C(26) 1.4016(15)
Ru(1) Cl(2) 2.3594(3) C(22) C(23) 1.3970(16)
Ru(1) N(2) 2.2969(9) C(22) C(27) 1.5059(16)
Ru(1) C(2) 2.0303(10) C(23) C(24) 1.3918(17)
Ru(1) C(38) 1.8325(11) C(24) C(25) 1.3936(18)
N(1) C(2) 1.3537(13) C(24) C(28) 1.5098(17)
N(1) C(5) 1.4723(15) C(25) C(26) 1.3966(16)
N(1) C(21) 1.4309(14) C(26) C(29) 1.5016(17)
N(2) C(37) 1.4897(14) C(31) C(32) 1.4124(15)
N(2) C(41) 1.4936(15) C(31) C(36) 1.4087(16)
N(2) C(45) 1.4872(14) C(31) C(38) 1.4547(15)
N(3) C(2) 1.3559(13) C(32) C(33) 1.3928(16)
N(3) C(4) 1.4670(14) C(32) C(37) 1.5023(17)
N(3) C(11) 1.4324(14) C(33) C(34) 1.389(2)
C(4) C(5) 1.5173(17) C(34) C(35) 1.384(2)
C(11) C(12) 1.4008(16) C(35) C(36) 1.3899(16)
C(11) C(16) 1.4051(15) C(41) C(42) 1.5189(16)
C(12) C(13) 1.3960(15) C(42) C(43) 1.5013(17)
C(12) C(17) 1.5062(16) C(43) C(44) 1.3922(17)
C(13) C(14) 1.3924(15) C(43) C(46) 1.4015(16)
C(14) C(15) 1.3939(15) C(44) C(45) 1.5090(16)
C(14) C(18) 1.5066(15) C(44) C(49) 1.3952(17)
C(15) C(16) 1.3962(15) C(46) C(47) 1.386(2)
C(16) C(19) 1.5103(16) C(47) C(48) 1.390(2)
C(21) C(22) 1.3945(16) C(48) C(49) 1.3876(18)
20
Table S13. Bond angles for 5d.

Cl(2) Ru(1) Cl(1) 163.605(10) C(15) C(16) C(19) 119.60(10)
N(2) Ru(1) Cl(1) 86.80(2) C(22) C(21) N(1) 118.59(10)
N(2) Ru(1) Cl(2) 91.75(2) C(22) C(21) C(26) 121.92(10)
C(2) Ru(1) Cl(1) 91.78(3) C(26) C(21) N(1) 119.43(10)
C(2) Ru(1) Cl(2) 87.48(3) C(21) C(22) C(23) 118.57(10)
C(2) Ru(1) N(2) 172.34(4) C(21) C(22) C(27) 121.01(10)
C(38) Ru(1) Cl(1) 101.32(4) C(23) C(22) C(27) 120.40(11)
C(38) Ru(1) Cl(2) 95.01(4) C(24) C(23) C(22) 121.15(11)
C(38) Ru(1) N(2) 90.23(4) C(23) C(24) C(25) 118.75(10)
C(38) Ru(1) C(2) 97.43(4) C(23) C(24) C(28) 119.66(12)
C(2) N(1) C(5) 113.51(9) C(25) C(24) C(28) 121.58(11)
C(2) N(1) C(21) 128.40(9) C(24) C(25) C(26) 122.04(11)
C(21) N(1) C(5) 117.28(9) C(21) C(26) C(29) 120.76(10)
C(37) N(2) Ru(1) 107.19(6) C(25) C(26) C(21) 117.51(11)
C(37) N(2) C(41) 107.44(8) C(25) C(26) C(29) 121.64(10)
C(41) N(2) Ru(1) 108.99(7) C(32) C(31) C(38) 124.33(10)
C(45) N(2) Ru(1) 117.67(7) C(36) C(31) C(32) 118.78(10)
C(45) N(2) C(37) 107.36(9) C(36) C(31) C(38) 116.89(10)
C(45) N(2) C(41) 107.77(9) C(31) C(32) C(37) 121.62(10)
C(2) N(3) C(4) 114.32(9) C(33) C(32) C(31) 118.86(11)
C(2) N(3) C(11) 125.72(9) C(33) C(32) C(37) 119.51(10)
C(11) N(3) C(4) 119.94(9) C(34) C(33) C(32) 121.45(12)
N(1) C(2) Ru(1) 134.05(7) C(35) C(34) C(33) 120.30(11)
N(1) C(2) N(3) 106.37(9) C(34) C(35) C(36) 119.20(12)
N(3) C(2) Ru(1) 119.41(7) C(35) C(36) C(31) 121.41(11)
N(3) C(4) C(5) 102.33(9) N(2) C(37) C(32) 112.60(9)
N(1) C(5) C(4) 103.13(9) C(31) C(38) Ru(1) 130.10(8)
C(12) C(11) N(3) 119.23(10) N(2) C(41) C(42) 109.97(9)
C(12) C(11) C(16) 120.88(9) C(43) C(42) C(41) 111.19(10)
C(16) C(11) N(3) 119.62(10) C(44) C(43) C(42) 119.27(10)
C(11) C(12) C(17) 121.84(10) C(44) C(43) C(46) 118.86(11)
C(13) C(12) C(11) 117.90(10) C(46) C(43) C(42) 121.87(11)
C(13) C(12) C(17) 120.11(10) C(43) C(44) C(45) 121.94(10)
C(14) C(13) C(12) 121.98(10) C(43) C(44) C(49) 119.82(11)
C(13) C(14) C(15) 118.35(10) C(49) C(44) C(45) 118.20(11)
C(13) C(14) C(18) 120.23(10) N(2) C(45) C(44) 114.89(9)
C(15) C(14) C(18) 121.43(10) C(47) C(46) C(43) 121.18(13)
C(14) C(15) C(16) 121.34(10) C(46) C(47) C(48) 119.61(12)
C(11) C(16) C(19) 121.82(10) C(49) C(48) C(47) 119.72(13)
C(15) C(16) C(11) 118.37(10) C(48) C(49) C(44) 120.80(13)
Table S14. Hydrogen bonds for 5d.

C(37) H(37B) Cl(1) 0.99 2.58 3.2870(12) 128.0
C(41) H(41A) Cl(1) 0.99 2.68 3.3280(12) 123.3
21
Figure S5. Solid-state crystal structure of compound 5e
Table S15. Bond lengths for 5e.

Atom Atom Length (Å) Atom Atom Length (Å) Atom Atom Length (Å)
Ru(1) C(38) 1.827(3) Ru(1A) C(38A) 1.820(3) Ru(1B) C(38B) 1.831(3)
Ru(1) C(2) 2.015(3) Ru(1A) C(2A) 2.027(3) Ru(1B) C(2B) 2.021(3)
Ru(1) N(2) 2.323(2) Ru(1A) N(2A) 2.329(2) Ru(1B) N(2B) 2.340(2)
Ru(1) Cl(1) 2.3668(7) Ru(1A) Cl(1A) 2.3584(7) Ru(1B) Cl(1B) 2.3582(7)
Ru(1) Cl(2) 2.3820(7) Ru(1A) Cl(2A) 2.3704(7) Ru(1B) Cl(2B) 2.3742(7)
O(1) C(44) 1.426(4) O(1A) C(44A) 1.425(4) O(1B) C(42B) 1.426(3)
O(1) C(42) 1.431(3) O(1A) C(42A) 1.427(4) O(1B) C(44B) 1.427(3)
N(1) C(2) 1.340(3) N(1A) C(2A) 1.331(3) N(1B) C(2B) 1.341(3)
N(1) C(21) 1.430(4) N(1A) C(21A) 1.435(4) N(1B) C(21B) 1.429(4)
N(1) C(5) 1.484(3) N(1A) C(5A) 1.479(3) N(1B) C(5B) 1.485(3)
N(2) C(37) 1.482(4) N(2A) C(45A) 1.485(4) N(2B) C(37B) 1.478(4)
N(2) C(41) 1.483(4) N(2A) C(37A) 1.488(4) N(2B) C(45B) 1.483(3)
N(2) C(45) 1.496(3) N(2A) C(41A) 1.492(3) N(2B) C(41B) 1.494(3)
N(3) C(2) 1.351(3) N(3A) C(2A) 1.353(3) N(3B) C(2B) 1.353(3)
N(3) C(11) 1.442(3) N(3A) C(11A) 1.433(3) N(3B) C(11B) 1.433(3)
22
N(3) C(4) 1.477(3) N(3A) C(4A) 1.473(3) N(3B) C(4B) 1.476(3)

C(4) C(5) 1.511(4) C(4A) C(5A) 1.529(4) C(4B) C(5B) 1.513(4)
C(11) C(16) 1.391(4) C(11A) C(12A) 1.391(4) C(11B) C(12B) 1.393(4)
C(11) C(12) 1.412(3) C(11A) C(16A) 1.420(3) C(11B) C(16B) 1.415(3)
C(12) C(13) 1.387(4) C(12A) C(13A) 1.397(4) C(12B) C(13B) 1.396(4)
C(12) C(17) 1.505(4) C(12A) C(17A) 1.510(4) C(12B) C(17B) 1.502(4)
C(13) C(14) 1.386(4) C(13A) C(14A) 1.385(4) C(13B) C(14B) 1.386(4)
C(14) C(15) 1.384(4) C(14A) C(15A) 1.388(4) C(14B) C(15B) 1.390(4)
C(14) C(18) 1.512(4) C(14A) C(18A) 1.514(4) C(14B) C(18B) 1.508(4)
C(15) C(16) 1.397(4) C(15A) C(16A) 1.382(4) C(15B) C(16B) 1.380(4)
C(16) C(19) 1.506(4) C(16A) C(19A) 1.490(4) C(16B) C(19B) 1.499(4)
C(21) C(26) 1.394(4) C(21A) C(22A) 1.396(4) C(21B) C(26B) 1.397(4)
C(21) C(22) 1.402(4) C(21A) C(26A) 1.398(4) C(21B) C(22B) 1.399(4)
C(22) C(23) 1.380(4) C(22A) C(23A) 1.380(4) C(22B) C(23B) 1.381(4)
C(22) C(27) 1.512(4) C(22A) C(27A) 1.497(4) C(22B) C(27B) 1.508(4)
C(23) C(24) 1.386(4) C(23A) C(24A) 1.391(4) C(23B) C(24B) 1.384(4)
C(24) C(25) 1.394(4) C(24A) C(25A) 1.395(4) C(24B) C(25B) 1.397(4)
C(24) C(28) 1.507(4) C(24A) C(28A) 1.504(4) C(24B) C(28B) 1.503(4)
C(25) C(26) 1.390(4) C(25A) C(26A) 1.383(4) C(25B) C(26B) 1.387(4)
C(26) C(29) 1.511(4) C(26A) C(29A) 1.511(4) C(26B) C(29B) 1.511(4)
C(31) C(32) 1.398(4) C(31A) C(36A) 1.399(4) C(31B) C(36B) 1.391(4)
C(31) C(36) 1.398(4) C(31A) C(32A) 1.405(4) C(31B) C(32B) 1.403(4)
C(31) C(38) 1.460(3) C(31A) C(38A) 1.471(3) C(31B) C(38B) 1.469(3)
C(32) C(33) 1.390(4) C(32A) C(33A) 1.386(4) C(32B) C(33B) 1.390(4)
C(32) C(37) 1.501(4) C(32A) C(37A) 1.500(4) C(32B) C(37B) 1.499(4)
C(33) C(34) 1.380(5) C(33A) C(34A) 1.380(4) C(33B) C(34B) 1.384(4)
C(34) C(35) 1.384(5) C(34A) C(35A) 1.378(4) C(34B) C(35B) 1.377(4)
C(35) C(36) 1.395(4) C(35A) C(36A) 1.388(4) C(35B) C(36B) 1.387(4)
C(41) C(42) 1.509(4) C(41A) C(42A) 1.503(4) C(41B) C(42B) 1.505(4)
C(44) C(45) 1.498(4) C(44A) C(45A) 1.509(4) C(44B) C(45B) 1.506(4)
Table S16. Bond angles for 5e.

C(38) Ru(1) C(2) 99.06(12) C(13A) C(14A) C(18A) 121.6(3)
C(38) Ru(1) N(2) 93.14(10) C(15A) C(14A) C(18A) 120.3(3)
C(2) Ru(1) N(2) 167.79(10) C(16A) C(15A) C(14A) 122.8(3)
C(38) Ru(1) Cl(1) 95.35(8) C(15A) C(16A) C(11A) 117.5(3)
C(2) Ru(1) Cl(1) 91.92(7) C(15A) C(16A) C(19A) 120.3(2)
N(2) Ru(1) Cl(1) 87.52(6) C(11A) C(16A) C(19A) 122.2(3)
C(38) Ru(1) Cl(2) 92.60(8) C(22A) C(21A) C(26A) 122.1(3)
C(2) Ru(1) Cl(2) 87.36(7) C(22A) C(21A) N(1A) 118.9(3)
N(2) Ru(1) Cl(2) 91.50(6) C(26A) C(21A) N(1A) 119.1(2)
Cl(1) Ru(1) Cl(2) 172.03(3) C(23A) C(22A) C(21A) 117.6(3)
C(44) O(1) C(42) 108.4(2) C(23A) C(22A) C(27A) 121.8(3)
C(2) N(1) C(21) 125.8(2) C(21A) C(22A) C(27A) 120.6(3)
C(2) N(1) C(5) 113.8(2) C(22A) C(23A) C(24A) 122.7(3)
C(21) N(1) C(5) 119.7(2) C(23A) C(24A) C(25A) 117.5(3)
C(37) N(2) C(41) 109.6(2) C(23A) C(24A) C(28A) 120.9(3)
C(37) N(2) C(45) 106.1(2) C(25A) C(24A) C(28A) 121.5(3)
C(41) N(2) C(45) 105.8(2) C(26A) C(25A) C(24A) 122.3(3)
23
C(37) N(2) Ru(1) 107.52(17) C(25A) C(26A) C(21A) 117.7(2)

C(41) N(2) Ru(1) 114.50(16) C(25A) C(26A) C(29A) 120.7(3)
C(45) N(2) Ru(1) 112.93(16) C(21A) C(26A) C(29A) 121.6(3)
C(2) N(3) C(11) 124.6(2) C(36A) C(31A) C(32A) 119.2(3)
C(2) N(3) C(4) 113.9(2) C(36A) C(31A) C(38A) 119.8(3)
C(11) N(3) C(4) 120.8(2) C(32A) C(31A) C(38A) 121.0(3)
N(1) C(2) N(3) 106.9(2) C(33A) C(32A) C(31A) 119.0(3)
N(1) C(2) Ru(1) 135.6(2) C(33A) C(32A) C(37A) 121.3(3)
N(3) C(2) Ru(1) 117.1(2) C(31A) C(32A) C(37A) 119.5(2)
N(3) C(4) C(5) 102.5(2) C(34A) C(33A) C(32A) 121.3(3)
N(1) C(5) C(4) 102.7(2) C(35A) C(34A) C(33A) 120.1(3)
C(16) C(11) C(12) 121.4(3) C(34A) C(35A) C(36A) 119.7(3)
C(16) C(11) N(3) 120.6(2) C(35A) C(36A) C(31A) 120.7(3)
C(12) C(11) N(3) 117.7(3) N(2A) C(37A) C(32A) 115.0(2)
C(13) C(12) C(11) 117.5(3) C(31A) C(38A) Ru(1A) 123.5(2)
C(13) C(12) C(17) 120.7(2) N(2A) C(41A) C(42A) 111.5(2)
C(11) C(12) C(17) 121.7(3) O(1A) C(42A) C(41A) 111.5(2)
C(14) C(13) C(12) 122.4(3) O(1A) C(44A) C(45A) 112.2(2)
C(15) C(14) C(13) 118.4(3) N(2A) C(45A) C(44A) 111.3(2)
C(15) C(14) C(18) 121.1(3) C(38B) Ru(1B) C(2B) 99.04(12)
C(13) C(14) C(18) 120.6(3) C(38B) Ru(1B) N(2B) 92.01(10)
C(14) C(15) C(16) 121.9(3) C(2B) Ru(1B) N(2B) 168.93(10)
C(11) C(16) C(15) 118.0(2) C(38B) Ru(1B) Cl(1B) 96.99(8)
C(11) C(16) C(19) 122.9(3) C(2B) Ru(1B) Cl(1B) 92.22(7)
C(15) C(16) C(19) 118.9(3) N(2B) Ru(1B) Cl(1B) 87.14(5)
C(26) C(21) C(22) 121.6(3) C(38B) Ru(1B) Cl(2B) 92.76(8)
C(26) C(21) N(1) 118.8(3) C(2B) Ru(1B) Cl(2B) 86.22(7)
C(22) C(21) N(1) 119.6(2) N(2B) Ru(1B) Cl(2B) 92.54(6)
C(23) C(22) C(21) 118.3(2) Cl(1B) Ru(1B) Cl(2B) 170.25(3)
C(23) C(22) C(27) 120.8(3) C(42B) O(1B) C(44B) 108.5(2)
C(21) C(22) C(27) 120.9(3) C(2B) N(1B) C(21B) 125.8(2)
C(22) C(23) C(24) 122.0(3) C(2B) N(1B) C(5B) 113.5(2)
C(23) C(24) C(25) 118.3(3) C(21B) N(1B) C(5B) 120.3(2)
C(23) C(24) C(28) 121.1(3) C(37B) N(2B) C(45B) 109.4(2)
C(25) C(24) C(28) 120.6(3) C(37B) N(2B) C(41B) 106.7(2)
C(26) C(25) C(24) 122.0(3) C(45B) N(2B) C(41B) 106.3(2)
C(25) C(26) C(21) 117.8(3) C(37B) N(2B) Ru(1B) 106.86(17)
C(25) C(26) C(29) 121.5(2) C(45B) N(2B) Ru(1B) 113.92(15)
C(21) C(26) C(29) 120.7(3) C(41B) N(2B) Ru(1B) 113.41(15)
C(32) C(31) C(36) 119.4(3) C(2B) N(3B) C(11B) 124.3(2)
C(32) C(31) C(38) 121.6(3) C(2B) N(3B) C(4B) 113.4(2)
C(36) C(31) C(38) 119.0(3) C(11B) N(3B) C(4B) 121.2(2)
C(33) C(32) C(31) 119.0(3) N(1B) C(2B) N(3B) 107.3(2)
C(33) C(32) C(37) 120.3(3) N(1B) C(2B) Ru(1B) 135.0(2)
C(31) C(32) C(37) 120.3(2) N(3B) C(2B) Ru(1B) 117.36(19)
C(34) C(33) C(32) 121.6(3) N(3B) C(4B) C(5B) 102.8(2)
C(33) C(34) C(35) 119.8(3) N(1B) C(5B) C(4B) 102.6(2)
C(34) C(35) C(36) 119.6(3) C(12B) C(11B) C(16B) 121.0(3)
C(35) C(36) C(31) 120.6(3) C(12B) C(11B) N(3B) 121.1(2)
N(2) C(37) C(32) 115.3(2) C(16B) C(11B) N(3B) 117.6(2)
C(31) C(38) Ru(1) 123.7(2) C(11B) C(12B) C(13B) 117.9(2)
N(2) C(41) C(42) 110.9(2) C(11B) C(12B) C(17B) 123.1(3)
24
O(1) C(42) C(41) 111.9(2) C(13B) C(12B) C(17B) 118.8(3)

O(1) C(44) C(45) 111.6(2) C(14B) C(13B) C(12B) 122.4(3)
N(2) C(45) C(44) 111.6(2) C(13B) C(14B) C(15B) 117.7(3)
C(38A) Ru(1A) C(2A) 98.64(12) C(13B) C(14B) C(18B) 122.0(3)
C(38A) Ru(1A) N(2A) 92.35(10) C(15B) C(14B) C(18B) 120.3(3)
C(2A) Ru(1A) N(2A) 169.00(10) C(16B) C(15B) C(14B) 122.6(3)
C(38A) Ru(1A) Cl(1A) 97.20(9) C(15B) C(16B) C(11B) 117.9(3)
C(2A) Ru(1A) Cl(1A) 91.10(7) C(15B) C(16B) C(19B) 120.5(2)
N(2A) Ru(1A) Cl(1A) 87.92(6) C(11B) C(16B) C(19B) 121.5(3)
C(38A) Ru(1A) Cl(2A) 92.51(9) C(26B) C(21B) C(22B) 121.7(3)
C(2A) Ru(1A) Cl(2A) 87.52(7) C(26B) C(21B) N(1B) 119.1(2)
N(2A) Ru(1A) Cl(2A) 91.60(6) C(22B) C(21B) N(1B) 119.2(3)
Cl(1A) Ru(1A) Cl(2A) 170.29(3) C(23B) C(22B) C(21B) 117.6(3)
C(44A) O(1A) C(42A) 108.3(2) C(23B) C(22B) C(27B) 121.7(2)
C(2A) N(1A) C(21A) 126.9(2) C(21B) C(22B) C(27B) 120.6(3)
C(2A) N(1A) C(5A) 113.7(2) C(22B) C(23B) C(24B) 122.8(3)
C(21A) N(1A) C(5A) 119.3(2) C(23B) C(24B) C(25B) 117.9(3)
C(45A) N(2A) C(37A) 109.4(2) C(23B) C(24B) C(28B) 121.1(3)
C(45A) N(2A) C(41A) 105.4(2) C(25B) C(24B) C(28B) 121.0(3)
C(37A) N(2A) C(41A) 106.3(2) C(26B) C(25B) C(24B) 121.7(3)
C(45A) N(2A) Ru(1A) 114.50(16) C(25B) C(26B) C(21B) 118.1(2)
C(37A) N(2A) Ru(1A) 107.64(17) C(25B) C(26B) C(29B) 120.6(3)
C(41A) N(2A) Ru(1A) 113.36(15) C(21B) C(26B) C(29B) 121.2(3)
C(2A) N(3A) C(11A) 123.3(2) C(36B) C(31B) C(32B) 119.4(3)
C(2A) N(3A) C(4A) 113.4(2) C(36B) C(31B) C(38B) 119.5(3)
C(11A) N(3A) C(4A) 121.4(2) C(32B) C(31B) C(38B) 121.1(2)
N(1A) C(2A) N(3A) 107.8(2) C(33B) C(32B) C(31B) 118.9(3)
N(1A) C(2A) Ru(1A) 134.5(2) C(33B) C(32B) C(37B) 121.7(3)
N(3A) C(2A) Ru(1A) 117.4(2) C(31B) C(32B) C(37B) 119.3(2)
N(3A) C(4A) C(5A) 102.5(2) C(34B) C(33B) C(32B) 121.1(3)
N(1A) C(5A) C(4A) 102.5(2) C(35B) C(34B) C(33B) 119.9(3)
C(12A) C(11A) C(16A) 120.9(3) C(34B) C(35B) C(36B) 119.8(3)
C(12A) C(11A) N(3A) 121.0(2) C(35B) C(36B) C(31B) 120.7(3)
C(16A) C(11A) N(3A) 117.9(3) N(2B) C(37B) C(32B) 113.3(2)
C(11A) C(12A) C(13A) 118.3(2) C(31B) C(38B) Ru(1B) 122.9(2)
C(11A) C(12A) C(17A) 123.0(3) N(2B) C(41B) C(42B) 111.0(2)
C(13A) C(12A) C(17A) 118.5(3) O(1B) C(42B) C(41B) 110.8(2)
C(14A) C(13A) C(12A) 121.8(3) O(1B) C(44B) C(45B) 112.5(2)
C(13A) C(14A) C(15A) 118.1(3) N(2B) C(45B) C(44B) 111.6(2)
Table S17. Hydrogen bonds for 5e.

C(4) H(4A) Cl(2A)1 0.99 2.69 3.504(3) 139.9
C(5) H(5B) Cl(2A) 1 0.99 2.92 3.618(3) 128.7
C(41) H(41B) Cl(2) 0.99 2.65 3.210(3) 116.0
C(42) H(42A) Cl(2) 0.99 2.75 3.389(3) 122.4
C(45) H(45A) Cl(1) 0.99 2.48 3.165(3) 126.1
C(4A) H(4AA) Cl(2B)2 0.99 2.82 3.581(3) 134.7
C(5A) H(5AB) Cl(2B) 2 0.99 2.80 3.574(3) 135.3
C(41A) H(41C) Cl(1A) 0.99 2.50 3.168(3) 124.5
25
C(44A) H(44C) Cl(2A) 0.99 2.79 3.423(3) 122.1

C(45A) H(45D) Cl(2A) 0.99 2.65 3.221(3) 116.6
C(4B) H(4BA) Cl(2)3 0.99 2.82 3.628(3) 139.6
C(41B) H(41E) Cl(1B) 0.99 2.51 3.185(3) 125.4
C(44B) H(44E) Cl(2B) 0.99 2.74 3.397(3) 124.5
C(45B) H(45F) Cl(2B) 0.99 2.68 3.235(3) 116.1
1+X,1/2-Y,-1/2+Z; 2+X,1/2-Y,1/2+Z; 31+X,1/2-Y,1/2+Z
Figure S6. Solid-state crystal structure of compound 5f
Table S18. Bond lengths for 5f.

Ru(1) C(38) 1.815(4) C(14) C(15) 1.371(6)
Ru(1) C(2) 2.027(5) C(14) C(18) 1.511(6)
Ru(1) N(2) 2.251(4) C(15) C(16) 1.403(6)
Ru(1) Cl(1) 2.3517(13) C(16) C(19) 1.498(6)
Ru(1) Cl(2) 2.3537(12) C(21) C(22) 1.396(6)
N(1) C(2) 1.347(5) C(21) C(26) 1.399(6)
N(1) C(21) 1.431(5) C(22) C(23) 1.394(6)
N(1) C(5) 1.473(6) C(22) C(27) 1.508(6)
N(2) C(41) 1.492(5) C(23) C(24) 1.380(6)
N(2) C(45) 1.493(5) C(24) C(25) 1.395(6)
N(2) C(37) 1.496(5) C(24) C(28) 1.499(6)
N(3) C(2) 1.360(5) C(25) C(26) 1.391(6)
N(3) C(11) 1.435(5) C(26) C(29) 1.509(6)
N(3) C(4) 1.472(6) C(31) C(32) 1.404(6)
N(4) C(46) 1.449(6) C(31) C(36) 1.409(6)
N(4) C(44) 1.453(5) C(31) C(38) 1.468(6)
N(4) C(42) 1.457(6) C(32) C(33) 1.391(6)
C(4) C(5) 1.515(6) C(32) C(37) 1.491(6)
C(11) C(16) 1.403(6) C(33) C(34) 1.385(7)
C(11) C(12) 1.403(6) C(34) C(35) 1.372(7)
C(12) C(13) 1.391(6) C(35) C(36) 1.373(6)
26
C(12) C(17) 1.508(6) C(41) C(42) 1.519(6)

C(13) C(14) 1.386(6) C(44) C(45) 1.519(6)
Table S19. Bond angles for 5f.

C(38) Ru(1) C(2) 99.31(19) C(15) C(14) C(13) 118.5(4)
C(38) Ru(1) N(2) 87.69(17) C(15) C(14) C(18) 120.8(4)
C(2) Ru(1) N(2) 172.84(16) C(13) C(14) C(18) 120.6(5)
C(38) Ru(1) Cl(1) 98.58(15) C(14) C(15) C(16) 122.2(4)
C(2) Ru(1) Cl(1) 88.11(13) C(11) C(16) C(15) 117.9(4)
N(2) Ru(1) Cl(1) 89.38(10) C(11) C(16) C(19) 122.2(4)
C(38) Ru(1) Cl(2) 100.49(15) C(15) C(16) C(19) 119.8(4)
C(2) Ru(1) Cl(2) 89.45(13) C(22) C(21) C(26) 121.7(4)
N(2) Ru(1) Cl(2) 90.75(10) C(22) C(21) N(1) 119.4(4)
Cl(1) Ru(1) Cl(2) 160.92(4) C(26) C(21) N(1) 118.9(4)
C(2) N(1) C(21) 127.9(4) C(23) C(22) C(21) 117.5(4)
C(2) N(1) C(5) 113.9(4) C(23) C(22) C(27) 120.8(4)
C(21) N(1) C(5) 117.6(4) C(21) C(22) C(27) 121.6(4)
C(41) N(2) C(45) 107.2(3) C(24) C(23) C(22) 123.0(5)
C(41) N(2) C(37) 110.9(3) C(23) C(24) C(25) 117.4(4)
C(45) N(2) C(37) 110.9(3) C(23) C(24) C(28) 121.9(5)
C(41) N(2) Ru(1) 104.2(3) C(25) C(24) C(28) 120.7(5)
C(45) N(2) Ru(1) 114.7(3) C(26) C(25) C(24) 122.4(4)
C(37) N(2) Ru(1) 108.8(3) C(25) C(26) C(21) 117.9(4)
C(2) N(3) C(11) 128.1(4) C(25) C(26) C(29) 121.1(4)
C(2) N(3) C(4) 113.8(4) C(21) C(26) C(29) 121.0(4)
C(11) N(3) C(4) 118.0(4) C(32) C(31) C(36) 118.6(4)
C(46) N(4) C(44) 110.8(4) C(32) C(31) C(38) 125.0(4)
C(46) N(4) C(42) 112.1(4) C(36) C(31) C(38) 116.4(4)
C(44) N(4) C(42) 109.7(4) C(33) C(32) C(31) 118.4(4)
N(1) C(2) N(3) 106.1(4) C(33) C(32) C(37) 119.0(4)
N(1) C(2) Ru(1) 131.3(3) C(31) C(32) C(37) 122.7(4)
N(3) C(2) Ru(1) 122.2(3) C(34) C(33) C(32) 122.0(5)
N(3) C(4) C(5) 102.2(4) C(35) C(34) C(33) 119.6(5)
N(1) C(5) C(4) 102.6(4) C(34) C(35) C(36) 119.8(5)
C(16) C(11) C(12) 121.0(4) C(35) C(36) C(31) 121.5(5)
C(16) C(11) N(3) 121.3(4) C(32) C(37) N(2) 112.7(4)
C(12) C(11) N(3) 117.5(4) C(31) C(38) Ru(1) 129.5(3)
C(13) C(12) C(11) 118.0(4) N(2) C(41) C(42) 113.7(4)
C(13) C(12) C(17) 119.8(4) N(4) C(42) C(41) 110.6(4)
C(11) C(12) C(17) 122.2(4) N(4) C(44) C(45) 110.2(4)
C(14) C(13) C(12) 122.3(5) N(2) C(45) C(44) 114.3(4)
Table S20. Hydrogen bonds in compound 5f.

C(5) H(5A) Cl(2)1 0.99 2.84 3.823(5) 172.4
C(37) H(37A) Cl(1) 0.99 2.49 3.188(5) 127.2
C(41) H(41B) Cl(1) 0.99 2.93 3.519(5) 119.2
27
C(41) H(41B) Cl(1)2 0.99 2.82 3.612(5) 137.9

C(45) H(45B) Cl(2) 0.99 2.49 3.201(5) 128.5
1-1/2+X,3/2-Y,-1/2+Z; 21-X,2-Y,2-Z
All complexes 5a−f form long intermolecular C─H…Cl hydrogen bonds and are packed due to these weak
interactions. The packing of the smallest molecules 5a and 5b is the same because they are isostructural: they
form 2D layer in (001) plane, solvent molecules occupy the space between these layers. Molecules 5f and 5e also
form 2D layers in (10–2) and (10–1) planes respectively. The larger molecules 5c and 5d form only dimers with
the same values of hydrogen C─H…Cl bonds which then pack in 3D framework for 5c and in 2D layers in (100)
plane for 5d due to weaker contacts. Packing of molecules 5 are given bellow (Figure S7).
5a View along [100]

28
5b View along [100]

29
5c View along [100]

30
5d View along [100]
5e View along [100]

31
5f View along [100]
Figure S7. Crystalline packing in compounds 5a, 5b, 5c, 5d, 5e, and 5f
32
References for Supporting Information
[1] SAINT-Plus, Version 7.68., Bruker AXS Inc., Madison, Wisconsin, USA.
[2] SADABS, Madison, Wisconsin (USA): Bruker AXS, 2008.
[3] Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Cryst. 2015, C71, 3–8.
[4] Dolomanov, O.V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: A Complete Structure
Solution, Refinement and Analysis Program. J. Appl. Cryst. 2009, 42, 339−341.
[5] Spek, A. L. PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the
calculated structure factors. Acta Cryst. 2015, C71, 9−18.
Figure S8. 1H NMR spectrum of compound 4f
Acquisition Time (sec) 1.9818 Comment single_pulse Date 30 Jun 1990 07:02:57
Date Stamp 09 Sep 2019 13:06:16 File Name C:\Users\Fedor\Desktop\09.09.19\FZ7795-1.jdf Frequency (MHz) 600.17
Nucleus 1H Number of Transients 8 Origin ECA 600 Original Points Count 32768 Owner delta
Points Count 32768 Pulse Sequence single_pulse.ex2 Receiver Gain 32.00 Solvent CHLOROFORM-
d
Spectrum Offset (Hz) 5408.1045 Sweep Width (Hz) 16534.39 Temperature (degree C) 21.400
CH2
2
3 1 3 CH3
4 2 2 N 1
4
5 1 N 5
6 1 1 6
2.27
FZ7795-1.jdf
3.51
7.26
7.20 7.21
5.29
5.66
5.27
5.63
7.51
7.53
7.27
7.18
2.26
2.46
0.00
1.00 4.17 1.00 1.01 2.05 6.88 3.59
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
d
CH2
2
3 1 3 CH3
4 2 2 N 1
4
5 1 N 5
6 1 1 6
FZ7795-1.jdf
7.26
7.21
5.29
5.66
5.27
5.63
7.51
7.24
7.53
7.27
7.20
7.22
7.18
1.00 4.17 1.00 1.01
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2
d
CH2
2
3 1 3 CH3
4 2 2 N 1
4
5 1 N 5
6 1 1 6
2.27
FZ7795-1.jdf
3.51
2.26
2.46
2.05 6.88 3.59
3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1
Figure S9. 13C NMR spectrum of compound 4f
Acquisition Time (sec) 0.6921 Comment single pulse decoupled gated NOE Date 30 Jun 1990 07:11:58
Date Stamp 09 Sep 2019 13:15:17 File Name C:\Users\Fedor\Desktop\09.09.19\FZ7795-2.jdf
Frequency (MHz) 150.91 Nucleus 13C Number of Transients 401 Origin ECA 600
Original Points Count 32768 Owner delta Points Count 32768 Pulse Sequence single_pulse_dec
Receiver Gain 58.00 Solvent CHLOROFORM-d Spectrum Offset (Hz) 15091.3428
Sweep Width (Hz) 47348.49 Temperature (degree C) 22.300
CH2
2
3 1 3 CH3
4 2 2 N 1
4
5 1 N 5
6 1 1 6
55.30
FZ7795-2.jdf
53.16
46.15
125.72
134.94
130.49
127.40
115.28
77.35
77.14
76.92
137.93
60.67
200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
CH2
2
3 1 3 CH3
4 2 2 N 1
4
5 1 N 5
6 1 1 6
FZ7795-2.jdf
125.72
134.94
130.49
127.40
115.28
127.45
137.93
135.44
138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121 120 119 118 117 116 115
CH2
2
3 1 3 CH3
4 2 2 N 1
4
5 1 N 5
6 1 1 6
55.30
FZ7795-2.jdf
53.16
46.15
77.35
77.14
76.92
60.67
78 76 74 72 70 68 66 64 62 60 58 56 54 52 50 48 46
Figure S10. 1H NMR spectrum of compound 5a 26.07.2019 16:26:14
Formula C H Cl N Ru FW 651.6758
33 41 2 3
Acquisition Time (sec) 2.5690 Comment FZ_Grubbs_FZ7431 in CD2Cl2 Date 28 Jun 2019 15:23:44
Date Stamp 28 Jun 2019 15:23:44
File Name D:\Desktop\Зай\ЯМР\2019 Июнь Граббсы Циклические + Двумерки для Лизы и Ксении\FZ_Grubbs_FZ7431_001001r
Frequency (MHz) 300.13 Nucleus 1H Number of Transients 46 Origin spect
Original Points Count 65536 Owner nmr Points Count 262144 Pulse Sequence zg
Receiver Gain 40.73 SW(cyclical) (Hz) 25510.20 Solvent DICHLOROMETHANE-d2
CH3 H3C
1 5 4 1
2 6 5
3
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
35 H3C
1 Cl Ru
2- 1
4 365 1
1
N 1 6
1
3 2 1 2 5
3 4
2.44
FZ_Grubbs_FZ7431_001001r.esp VerticalScaleFactor = 1
7.08
4.11
2.53
18.84
4.26
5.36
5.36
7.03
6.76
7.53
7.22
7.00
6.73
2.76
1.50
1.33
2.14
2.15
1.51
1.33
1.31
2.78
2.12
7.55
2.80
1.26
0.99 1.16 1.10 4.00 2.35 2.20 4.45
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
26.07.2019 16:26:32
33 41 2 3
Date Stamp 28 Jun 2019 15:23:44
CH3 H3C
1 5 4 1
2 6 5
3
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
35 H3C
1 Cl Ru
2- 1
4 365 1
1
N 1 6
1
3 2 1 2 5
3 4
FZ_Grubbs_FZ7431_001001r.esp
7.08
VerticalScaleFactor = 1
7.03
6.76
7.53
7.22
7.53
7.00
6.73
7.50
7.50
7.24
7.19
7.55
7.55
1.12 1.16 5.24 1.10
7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65
26.07.2019 16:26:51
33 41 2 3
Date Stamp 28 Jun 2019 15:23:44
CH3 H3C
1 5 4 1
2 6 5
3
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
35 H3C
1 Cl Ru
2- 1
4 365 1
1
N 1 6
1
3 2 1 2 5
3 4
2.44
4.11
2.53
4.26
2.76
1.50
1.33
2.14
2.15
2.75
1.51
1.33
1.26 1.31
2.78
2.12
1.35
1.47
2.73
2.24
2.17
1.52
2.80
2.10
1.43
1.39
2.01 4.00 2.35 17.33 2.20 4.45
4.0 3.5 3.0 2.5 2.0 1.5

Figure S11. 13C NMR spectrum of compound 5a 26.07.2019 16:38:53
33 41 2 3
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_FZ7431-C13dec [hp-dec] Date 28 Jun 2019 16:40:32
Date Stamp 28 Jun 2019 16:40:32
Frequency (MHz) 75.47 Nucleus 13C Number of Transients 1280 Origin spect
Original Points Count 65536 Owner nmr Points Count 262144 Pulse Sequence zgpg
CH3 H3C
1 5 4 1
2 6 5
3
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
35 H3C
1 Cl Ru
2- 1
4 365 1
1
N 1 6
1
3 2 1 2 5
3 4
129.20
FZ_Grubbs_FZ7431_013001r VerticalScaleFactor = 1
23.12
56.40
53.45
128.75
128.05
126.14
130.73
20.80
53.09
63.23
138.44
312.57
133.85
52.73
149.17
212.82
51.47
19.29
138.63
138.86
136.26
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
26.07.2019 16:39:28
33 41 2 3
Date Stamp 28 Jun 2019 16:40:32
CH3 H3C
1 5 4 1
2 6 5
3
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
35 H3C
1 Cl Ru
2- 1
4 365 1
1
N 1 6
1
3 2 1 2 5
3 4
129.20
128.75
128.05
126.14
130.73
138.44
133.85
149.17
138.63
138.86
136.26
149 148 147 146 145 144 143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125
26.07.2019 16:39:48
33 41 2 3
Date Stamp 28 Jun 2019 16:40:32
CH3 H3C
1 5 4 1
2 6 5
3
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
35 H3C
1 Cl Ru
2- 1
4 365 1
1
N 1 6
1
3 2 1 2 5
3 4
23.12
56.40
53.45
20.80
53.81
53.09
63.23
52.73
54.17
51.47
19.29
64 62 60 58 56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16 14
Figure S12. NMR DEPT135 spectrum of compound 5a
26.07.2019 16:44:33
33 41 2 3
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_FZ7431-dept135 [hp-dec] Date 28 Jun 2019 16:17:04
Date Stamp 28 Jun 2019 16:17:04
Original Points Count 65536 Owner nmr Points Count 262144 Pulse Sequence dept135
CH3 H3C
1 5 4 1
2 6 5
3
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
35 H3C
1 Cl Ru
2- 1
4 365 1
1
N 1 6
1
3 2 1 2 5
3 4
129.20
FZ_Grubbs_FZ7431_015001r VerticalScaleFactor = 1
126.14
128.05
130.73
312.57
128.74
20.78
19.36
51.48
63.22
23.12
56.40
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
Figure S13. 1H NMR COSY spectrum of compound 5a
33 41 2 3
FZ_Grubbs_FZ7431.011.001.2rr.esp CH3 H3C

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
0 5 Cl
35 H3C
1
H3C Cl 2- 1
1
365 Ru 1
4 1
2
N 1 6
3 1
3 2 1 2 5
4
3 4
5
F1 Chemical Shift (ppm)

8
10
11
12
13
14
15
16
17
18
19
18 16 14 12 10 8 6 4 2 0
33 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
35 H3C
2.5 H3C Cl 2- 1
1
365 Ru 1
4 1
3.0 N 1 6
1
3 2 1 2 5
3.5 3 4
4.0

4.5
5.0
5.5
6.0
6.5
7.0
7.5
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7

33 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
0.9
35 H3C
H3C Cl 2- 1
1.0 1
365 Ru 1
4 1
1.1
N 1 6
1.2 1
3 2 1 2 5
1.3
3 4
1.4
1.5
1.6
1.7

1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.0 2.5 2.0 1.5

Figure S14. NMR HSQC spectrum of compound 5a
33 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
0 35 H3C
H3C Cl 2- 1
1
365 Ru 1
20 4 1
40
N 1 6
1
3 2 1 2 5
60
3 4
80
100
120

140
160
180
200
220
240
260
280
300
320
18 16 14 12 10 8 6 4 2 0
1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
35 H3C
125.0 H3C Cl 2- 1
1
365 Ru 1
4 1
125.5
6.73, 125.92, 0.15 N 1 6
1
126.0 3 2 1 2 5
6.76, 125.92, 0.15
3 4
126.5
127.0
7.53, 127.69, 0.14

127.5

7.24, 128.57, 0.09 128.0
7.2, 128.57, 0.09
128.5
7.22, 128.57, 0.14
129.0
7.08, 129.01, 1
129.5
130.0
7.01, 130.77, 0.13 130.5
7.02, 130.77, 0.13 131.0
131.5
132.0
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7
1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
15 35 H3C
H3C Cl 2- 1
2.53, 19.32, 0.14 1
365 Ru 1
2.44, 20.21, 0.27 4 1
20 N 1 6
1.5, 22.85, 0.1
1
3 2 1 2 5
1.32, 22.85, 0.1
25 3 4
30

35
40
45
4.12, 51.04, 0.37

50
2.76, 56.33, 0.11 2.14, 56.33, 0.12

55
60
4.26, 62.93, 0.22
65
4.0 3.5 3.0 2.5 2.0 1.5

Figure S15. NMR HMBC spectrum of compound 5a
33 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
0 5 Cl
35 H3C
H3C Cl 2- 1
20 1
365 Ru 1
4 1
40 N 1 6
1
3 2 1 2 5
60
3 4
80
100
120

140
160
180
200
220
240
260
280
300
18 16 14 12 10 8 6 4 2 0
33 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
124 35 H3C
H3C Cl 2- 1
1
365 Ru 1
4 1
126
N 1 6
1
128
3 2 1 2 5
3 4
130
132
134

136
138
140
142
144
146
148
150
18.87 18.86 18.85 18.84 18.83 18.82 18.81 18.80

33 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
35 H3C
126 H3C Cl 2- 1
1
365 Ru 1
4 1
128
N 1 6
1
3 2 1 2 5
130
3 4
132
134

136
138
140
142
144
146
148
150
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7
33 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
20
35 H3C
H3C Cl 2- 1
30 1
365 Ru 1
4 1
40
N 1 6
1
50 2 1
3 2 5
60 3 4
70
80
90

100
110
120
130
140
150
160
170
180
190
200
210
4.5 4.0 3.5 3.0 2.5 2.0 1.5

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
35 H3C
124 H3C Cl 2- 1
7.52, 125.92, 0.09 1
365 Ru 1
4 1
126
7.53, 125.92, 0.09 6.74, 128.13, 0.12 N 1 6
7.02, 128.57, 0.12 1
128 3 2 1 2 5
7.23, 130.33, 0.09
3 4
7.34, 129.01, 0.07 7.08, 129.01, 0.27 6.82, 129.01, 0.07
130
7.21, 130.33, 0.09
7.53, 133.41, 0.1 132
6.75, 133.41, 0.12 134

7.52, 133.85, 0.1 7.09, 136.06, 0.05

136
7.08, 136.06, 0.05
138
140
142
144
146
7.23, 148.83, 0.1 7.01, 148.83, 0.12

148
7.21, 148.83, 0.1

150
152
7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6
Figure S16. 1H NMR spectrum of compound 5b
26.07.2019 15:51:53
34 43 2 3
Date Stamp 28 Jun 2019 13:02:56
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
36 H3C
1 Cl Ru
2- 1
5 376 1
1
4 N 1 6
1
3 2 1 2 5
3 4
2.44
7.08
4.11
2.52
4.47
18.75
5.36
7.22 7.10
2.28
7.52
1.60
1.09
2.24
6.74
1.55
0.97
6.72
1.03
0.99
3.43
3.45
3.41
1.00 1.42 1.06 4.18 24.34 5.434.10
21 20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1
26.07.2019 15:52:13
34 43 2 3
Date Stamp 28 Jun 2019 13:02:56
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
36 H3C
1 Cl Ru
2- 1
5 376 1
1
4 N 1 6
1
3 2 1 2 5
3 4
7.08
7.10
7.52
7.22
6.74
6.72
7.50
7.24
7.20
1.42 6.38 1.06
7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65 6.60
26.07.2019 15:52:40
34 43 2 3
Date Stamp 28 Jun 2019 13:02:56
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
36 H3C
1 Cl Ru
2- 1
5 376 1
1
4 N 1 6
1
3 2 1 2 5
3 4
2.44
4.11
2.52
2.49
4.47
2.28
1.60
1.09
2.24
1.55
0.97
1.03
2.32
0.99
3.43
1.53
1.17
0.94
1.42
1.40
3.45
3.41
2.14 4.18 24.34 5.43 4.10
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

Figure S17. 13C NMR spectrum of compound 5b
26.07.2019 19:03:27
34 43 2 3
Date Stamp 28 Jun 2019 11:56:48
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
36 H3C
1 Cl Ru
2- 1
5 376 1
1
4 N 1 6
1
3 2 1 2 5
3 4
53.47
129.20
19.70
53.11
51.12
53.83
20.78
128.52
128.25
131.07
125.18
23.40
54.19
55.31
138.41
313.88
133.14
149.29
212.97
19.14
138.85
136.56
340 320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0 -20
26.07.2019 19:03:56
34 43 2 3
Date Stamp 28 Jun 2019 11:56:48
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
36 H3C
1 Cl Ru
2- 1
5 376 1
1
4 N 1 6
1
3 2 1 2 5
3 4
129.20
128.52
128.25
131.07
125.18
138.41
133.14
149.29
138.85
131.87
136.56
135.55
150 149 148 147 146 145 144 143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123
26.07.2019 19:04:27
34 43 2 3
Date Stamp 28 Jun 2019 11:56:48
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
36 H3C
1 Cl Ru
2- 1
5 376 1
1
4 N 1 6
1
3 2 1 2 5
3 4
53.47
19.70
53.11
51.12
53.83
20.78
23.40
52.75
54.19
55.31
51.52
19.14
56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16
Figure S18. NMR DEPT135 spectrum of compound 5b
26.07.2019 19:45:51
34 43 2 3
Date Stamp 28 Jun 2019 12:35:12
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
36 H3C
1 Cl Ru
2- 1
5 376 1
1
4 N 1 6
1
3 2 1 2 5
3 4
129.20
131.07
125.18
128.52
128.25
20.78
313.87
53.67
53.31
54.03 51.37
23.39
55.32
19.70
51.12
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20
26.07.2019 19:46:28
34 43 2 3
Date Stamp 28 Jun 2019 12:35:12
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
36 H3C
1 Cl Ru
2- 1
5 376 1
1
4 N 1 6
1
3 2 1 2 5
3 4
129.20
131.07
125.18
128.52
128.25
20.78
53.67
53.31
54.03
51.37
23.39
55.32
19.70
51.12
130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15
Figure S19. NMR COSY spectrum of compound 5b
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
1 36 H3C
H3C Cl 2- 1
1
376 Ru 1
2 5 1
3
4 N 1 6
1
3 2 1 2 5
4
3 4
5

8
10
11
12
13
14
15
16
17
18
18 16 14 12 10 8 6 4 2
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
6.5
36 H3C
H3C Cl 2- 1
1
376 Ru 1
5 1
7.19, 6.7, 0.04 6.6
7.24, 6.7, 0.05 6.72, 6.7, 0.12 4 N 1 6
6.74, 6.73, 0.14 1
6.7 3 2 1 2 5
3 4
6.8
6.9

7.08, 7.05, 1 7.0
7.5, 7.11, 0.06
7.19, 7.2, 0.05 7.11, 7.08, 0.1 6.72, 7.2, 0.07 7.1
7.22, 7.2, 0.1 6.74, 7.2, 0.07
7.2
7.24, 7.2, 0.05
7.3
7.4
7.5, 7.49, 0.06 7.19, 7.49, 0.04
7.52, 7.52, 0.11 7.11, 7.52, 0.06
7.5
7.24, 7.52, 0.04 7.08, 7.52, 0.04
7.6
7.7
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
36 H3C
H3C Cl 2- 1
1.6, 1.04, 0.03 0.97, 0.95, 0.05
1
376 Ru 1
5 1
1.65, 1.04, 0.03 1.09, 1.07, 0.04
1.0 4 N 1 6
1
3 2 1 2 5
3 4
1.03, 1.59, 0.02

1.5

2.0
2.43, 2.24, 0.05 2.45, 2.24, 0.05
2.49, 2.44, 0.06

2.28, 2.27, 0.05
2.43, 2.42, 0.76 2.5

2.54, 2.5, 0.02
3.0
3.43, 3.41, 0.04 3.5
3.5 3.0 2.5 2.0 1.5 1.0

Figure S20. NMR HSQC spectrum of compound 5b
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
0 5 Cl
36 H3C
H3C Cl 2- 1
20 1 Ru
5 376 1
1
40 4 N 1 6
1
60 3 2 1 2 5
3 4
80
100
120

140
160
180
200
220
240
260
280
300
320
20 18 16 14 12 10 8 6 4 2 0
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
124.0
36 H3C
H3C Cl 2- 1
6.72, 125.04, 0.17 1 Ru
124.5 376 1
6.74, 125.04, 0.17 5 1
125.0 4 N 1 6
1
125.5 3 2 1 2 5
3 4
126.0
126.5
127.0

7.53, 128.13, 0.17 127.5
7.22, 128.13, 0.17
128.0
128.5
129.0
7.08, 129.01, 1
129.5
130.0
130.5
131.0
7.11, 131.21, 0.15 131.5
132.0
132.5
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
14 5 Cl
36 H3C
16 H3C Cl 2- 1
1
376 Ru 1
2.51, 19.77, 0.14 1.08, 19.77, 0.09 5 1
18
20
4 N 1 6
1.05, 19.77, 0.09 1
2.44, 20.21, 0.31 3 2 1 5
22 2
2.44, 21.97, -0.05
1.53, 22.85, 0.06 24 3 4
26
28
30

32
34
36
38
40
42
44
46
2.28, 50.6, 0.11 48

4.11, 51.04, 0.36 2.49, 51.04, 0.12
50
2.45, 51.04, 0.1 2.24, 51.04, 0.11 52
5.36, 53.24, 0.1 54
4.47, 55, 0.31 56
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
Figure S21. NMR HMBC spectrum of compound 5b
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
7.08, 20.65, 0.56 2.22, 20.65, 0.09 1 6 2 3 1
5 Cl
36 H3C
20 H3C Cl 2- 1
2.64, 20.65, 0.09 1
376 Ru 1
4.47, 51.04, 0.32 5 1
40
4 N 1 6
1
7.09, 55, 0.12 60
3 2 1 2 5
80 3 4
100
6.73, 128.13, 0.16
18.75, 125.04, 0.28
6.73, 132.97, 0.2 2.44, 129.01, 1
120

18.75, 132.97, 0.37 4.47, 132.53, 0.42 140
18.74, 149.27, 0.14 7.09, 149.27, 0.18 4.47, 149.27, 0.23

160
180
200
18.75, 212.7, 0.09 4.11, 212.7, 0.2 220
240
260
280
6.73, 314.02, 0.16 300
18 16 14 12 10 8 6 4 2
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
125 36 H3C
H3C Cl 2- 1
18.75, 132.97, 0.37 1
376 Ru 1
130 5 1
135 4 N 1 6
1
3 2 1 2 5
140
3 4
18.77, 149.27, 0.14 18.74, 149.27, 0.14 145
150
155

160
165
170
175
180
185
190
195
200
205
210
18.75, 212.7, 0.09 215
18.85 18.80 18.75 18.70 18.65

34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
18 36 H3C
7.08, 20.65, 0.56 2.22, 20.65, 0.09 H3C Cl 2- 1
20
1
376 Ru 1
5 1
2.64, 20.65, 0.09 22 4 N 1 6
1
7.08, 23.29, 0.05 24 3 2 1 2 5
26 3 4
28
30
32

34
36
38
40
42
44
46
48
4.47, 51.04, 0.32
50
52
7.09, 55, 0.12
54
56
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0
34 43 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
122
36 H3C
2.43, 124.6, 0.04 H3C Cl 2- 1
7.52, 125.04, 0.15
124
1
376 Ru 1
5 1
2.44, 126.36, 0.08
7.23, 128.13, 0.06 126
4 N 1 6
6.73, 128.13, 0.16 4.47, 128.13, 0.03 1
3 2 1 2 5
2.49, 129.01, 0.08
128
3 4
7.08, 129.01, 0.38 2.44, 129.01, 1 130
7.52, 132.97, 0.17

132
2.43, 131.65, 0.06
4.47, 132.53, 0.42
6.73, 132.97, 0.2 134

2.43, 133.41, 0.04
2.43, 135.17, 0.05 136
138
2.43, 138.26, 0.67
140
2.44, 140.9, 0.05

142
144
146
7.22, 149.27, 0.16 148
7.09, 149.27, 0.18 4.47, 149.27, 0.23 150
152
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5
Figure S22. 1H NMR spectrum of compound 5c
27.07.2019 13:00:50
37 41 2 3
Acquisition Time (sec) 2.5690 Comment FZ_Grubbs_10-K9 in CD2Cl2 Date 04 Jul 2019 19:07:44
Date Stamp 04 Jul 2019 19:07:44 File Name D:\Desktop\Зай\ЯМР\FZ_Grubbs_10-K9_001001r Frequency (MHz) 300.13
Nucleus 1H Number of Transients 64 Origin spect Original Points Count 65536 Owner nmr
Points Count 262144 Pulse Sequence zg Receiver Gain 72.88 SW(cyclical) (Hz) 25510.20
Solvent DICHLOROMETHANE-d2 Spectrum Offset (Hz) 1350.5919 Sweep Width (Hz) 25510.11 Temperature (degree C) 29.993
CH3 H3C
1 5 4 1
3 2 6 5
N N 1
1 1 3
H3C 4 C 4
CH3
1 6 2 2
5 Cl 3 1
H3C 39 H3C
Cl 2- 1
71 40 Ru
1 1 1
6 7a
N 1 6
5 3a 2
3 1 2 5
4
3 4
2.46
FZ_Grubbs_10-K9_001001r VerticalScaleFactor = 1
2.51
4.13
7.09
18.77
5.36
7.18
3.93
3.56
7.06
7.28 7.19
7.19
7.04
7.20
3.98
3.51
4.42
7.03
6.83
7.52
6.93
1.35
1.00 1.14 2.19 2.01 2.06 2.02 18.20
19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
27.07.2019 13:01:23
37 41 2 3
CH3 H3C
1 5 4 1
3 2 6 5
N N 1
1 1 3
H3C 4 C 4
CH3
1 6 2 2
5 Cl 3 1
H3C 39 H3C
Cl 2- 1
71 40 Ru
1 1 1
6 7a
N 1 6
5 3a 2
3 1 2 5
4
3 4
7.09
7.18
7.06
7.19
7.19
7.04
7.20
7.04
7.03
7.25
6.83
7.52
6.93
6.80
6.90
7.28
7.23
7.50
7.54
7.22
7.16
7.30
1.14 3.58 6.04 2.19
7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75
27.07.2019 13:01:43
37 41 2 3
CH3 H3C
1 5 4 1
3 2 6 5
N N 1
1 1 3
H3C 4 C 4
CH3
1 6 2 2
5 Cl 3 1
H3C 39 H3C
Cl 2- 1
71 40 Ru
1 1 1
6 7a
N 1 6
5 3a 2
3 1 2 5
4
3 4
2.46
2.51
4.13
3.93
3.56
3.98
3.51
4.42
2.01 4.14 2.06 2.02 18.20
4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3
Figure S23. 13C NMR spectrum of compound 5c
27.07.2019 13:17:20
37 41 2 3
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_10-K9-C13dec [hp-dec] Date 04 Jul 2019 19:33:20
Date Stamp 04 Jul 2019 19:33:20 File Name D:\Desktop\Зай\ЯМР\FZ_Grubbs_10-K9_013001r
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
39 H3C
Cl 2- 1
7
1
401 Ru 1
1
6 7a
N 1 6
5 3a 2
3 1 2 5
4
3 4
129.25
127.00
122.77
53.45
59.89
53.09
53.81
20.83
131.19
138.43
311.19
61.40
52.72
54.17
51.55
133.56
148.90
212.92
19.23
138.81
136.19
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
27.07.2019 13:17:56
37 41 2 3
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
39 H3C
Cl 2- 1
7
1
401 Ru 1
1
6 7a
N 1 6
5 3a 2
3 1 2 5
4
3 4
129.25
FZ_Grubbs_10-K9_013001r.esp VerticalScaleFactor = 1
127.00
122.77
128.84
126.64
128.32
131.19
138.43
137.83
133.56
148.90
138.81
136.19
149 148 147 146 145 144 143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122
27.07.2019 13:18:29
37 41 2 3
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
39 H3C
Cl 2- 1
7
1
401 Ru 1
1
6 7a
N 1 6
5 3a 2
3 1 2 5
4
3 4
FZ_Grubbs_10-K9_013001r.esp VerticalScaleFactor = 1
53.45
59.89
53.09
53.81
20.83
61.40
52.72
54.17
51.55
19.23
62 60 58 56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18
Figure S24. NMR DEPT135 spectrum of compound 5c
27.07.2019 13:44:21
37 41 2 3
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_10-K9-dept135 [hp-dec] Date 04 Jul 2019 21:09:20
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
39 H3C
Cl 2- 1
7
1
401 Ru 1
1
6 7a
N 1 6
5 3a 2
3 1 2 5
4
3 4
129.25
127.00
122.77
131.19
311.19
20.83
19.29
53.6651.55
61.40
59.89
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
27.07.2019 13:44:48
37 41 2 3
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_10-K9-dept135 [hp-dec] Date 04 Jul 2019 21:09:20
CH3 H3C
1 5 4 1
2 6
3 5
1
N N 1
1 3
H3C
4 C 4
CH3
6 2 2
1 5 3 1
Cl
H3C
39 H3C
Cl 2- 1
7
1
401 Ru 1
1
6 7a
N 1 6
5 3a 2
3 1 2 5
4
3 4
129.25
127.00
122.77
131.19
126.64
128.84
20.83
19.29
53.66
51.55
61.40
59.89
130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20

Figure S25. NMR COSY spectrum of compound 5c
37 41 2 3
FZ_Grubbs_10-K9.011.001.2rr.esp CH3 H3C

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
01 6 2 3 1
5 Cl
39 H3C
1 H3C Cl 2- 1
71 40 Ru 1
1 1
2 6 7a
N 1 6
3 5 3a 2
3 1 2 5
4
4
3 4
5

8
10
11
12
13
14
15
16
17
18
19
18 16 14 12 10 8 6 4 2
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
39 H3C
6.6 H3C Cl 2- 1
71 40 Ru 1
1 1
6 7a
6.7 N 1 6
5 3a 2
3 1 2 5
4
6.8 3 4
6.9
7.0

7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8

37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
3.3 39 H3C
H3C Cl 2- 1
71 40 Ru 1
1 1
3.4 6 7a
N 1 6
5 3a 2
3 1 2 5
3.5 4
3 4
3.6
3.7

3.8
3.9
4.0
4.1
4.2
4.3
4.4
4.5
4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5
Figure S26. NMR HSQC spectrum of compound 5c
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
0
5 Cl
39 H3C
H3C Cl 2- 1
20 71 40 Ru 1
1 1
6 7a
40 N 1 6
5 3a 2
3 1 2 5
60 4
3 4
80
100
120

140
160
180
200
220
240
260
280
300
320
18 16 14 12 10 8 6 4 2
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1201 6 2 3 1
5 Cl
39 H3C
121 H3C Cl 2- 1
71 40 Ru 1
7.04, 122.84, 0.15 122
1 1
6 7a
123
N 1 6
5 3a 2
3 1 2 5
124 4
3 4
125
7.18, 126.81, 0.26 6.8, 126.36, 0.15
7.19, 126.81, 0.26 126
6.83, 126.36, 0.15 127
128

7.26, 128.57, 0.14 129
7.09, 129.01, 1
130
6.93, 131.21, 0.14
131
6.91, 131.21, 0.15
132
133
134
135
136
137
138
139
140
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8

37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
49 39 H3C
H3C Cl 2- 1
71 40 Ru 1
50 1 1
6 7a
4.14, 51.04, 0.41
N 1 6
51 5 3a 2
3 1 2 5
4
52 3 4
53
54

55
56
57
58
3.98, 59.41, 0.14
3.93, 59.41, 0.19 3.51, 59.41, 0.18
59
3.56, 59.41, 0.15

60
61
4.42, 61.17, 0.11
62
63
4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
14.0 39 H3C
H3C Cl 2- 1
14.5 71 40 Ru 1
1 1
6 7a
15.0
N 1 6
5 3a 2
15.5 3 1 2 5
4
16.0 3 4
16.5
17.0
17.5

18.0
18.5
2.51, 19.32, 0.32
19.0
19.5
2.46, 20.21, 0.3
20.0
20.5
21.0
21.5
22.0
22.5
23.0
23.5
2.55 2.50 2.45 2.40

Figure S27. NMR HMBC spectrum of compound 5c
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
7.09, 18.88, 0.06 01 6 2 3 1
5 Cl
7.09, 20.65, 0.27 2.25, 20.65, 0.1
39 H3C
H3C Cl 2- 1
20
71 40 Ru 1
2.67, 20.65, 0.09 1 1
6 7a
40
6.91, 61.17, 0.06
3.56, 59.41, 0.07 N 1 6
5 3a 2
3 1 2 5
60 4
3.97, 61.17, 0.1
3 4
80
100
7.53, 126.36, 0.08
18.77, 126.36, 0.15 7.51, 126.36, 0.08 2.46, 129.01, 1
7.53, 133.41, 0.08 120

3.98, 122.4, 0.03
18.77, 133.41, 0.19 7.51, 133.41, 0.08 140
2.46, 138.26, 0.66
18.76, 148.83, 0.09 6.92, 148.83, 0.09
160
180
200
18.77, 212.7, 0.05 4.14, 212.7, 0.19 220
240
260
280
300
6.82, 310.93, 0.07 6.8, 311.37, 0.07

18 16 14 12 10 8 6 4 2
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
18.77, 126.36, 0.15 1 6 2 3 1
5 Cl
125 39 H3C
H3C Cl 2- 1
18.77, 133.41, 0.19
130 71 40 Ru 1
1 1
6 7a
135 N 1 6
5 3a 2
140 3 1 2 5
4
18.79, 148.83, 0.08 18.76, 148.83, 0.09 3 4
145
150
155
160

165
170
175
180
185
190
195
200
205
210
18.77, 212.7, 0.05 215
18.81 18.80 18.79 18.78 18.77 18.76 18.75 18.74 18.73 18.72 18.71
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
4.14, 212.7, 0.19 1 6 2 3 1
5 Cl
210
39 H3C
H3C Cl 2- 1
215 Ru
71 40
1 1
1
220 6 7a
N 1 6
225 5 3a 2
3 1 2 5
4
230
3 4
235
240
245
250

255
260
265
270
275
280
285
290
295
300
6.82, 310.93, 0.07 305
310
315
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5

Acquisition Time (sec) (0.3408, 0.0188) Comment 5 mm PABBO BB-1H/D Z-GRD Z104275/0345 Date 05 Jul 2019 09:58:00
File Name D:\Desktop\Зай\ЯМР\FZ_Grubbs_10-K9\213\pdata\1\2rr Frequency (MHz) (300.13, 75.48) Nucleus (1H, 13C)
Number of Transients 8 Origin spect Original Points Count (3072, 640) Owner nmr
Points Count (8192, 1024) Pulse Sequence hmbcgplpndqf Solvent CD2Cl2 Sweep Width (Hz) (9014.42, 34013.61)
Temperature (degree C) 29.984 Title FZ_Grubbs_10-K9-HMBC
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
H3C 2 CH3
1 6 2 3 1
5 Cl
39 H3C
120 H3C Cl 2- 1
71 40 Ru 1
7.2, 122.4, 0.06 1 1
6 7a
122
N 1 6
5 3a 2
7.17, 122.84, 0.06 3 1 2 5
124 4
3 4
7.04, 126.81, 0.12
126

128
7.09, 129.01, 0.18

130
132
134
7.09, 136.06, 0.08
7.19, 137.38, 0.04 136

7.06, 137.82, 0.05
138
7.02, 137.82, 0.05
140
7.20 7.15 7.10 7.05 7.00

Acquisition Time (sec) (0.3408, 0.0188) Comment 5 mm PABBO BB-1H/D Z-GRD Z104275/0345 Date 05 Jul 2019 09:58:00
File Name D:\Desktop\Зай\ЯМР\FZ_Grubbs_10-K9\213\pdata\1\2rr Frequency (MHz) (300.13, 75.48) Nucleus (1H, 13C)
Number of Transients 8 Origin spect Original Points Count (3072, 640) Owner nmr
Points Count (8192, 1024) Pulse Sequence hmbcgplpndqf Solvent CD2Cl2 Sweep Width (Hz) (9014.42, 34013.61)
Temperature (degree C) 29.984 Title FZ_Grubbs_10-K9-HMBC
37 41 2 3

1 5 4 1
2 6 5
3
1
N N 1
4 1 C 3 4
122 H3C 2 CH3
1 6 2 3 1
5 Cl
39 H3C
124 H3C Cl 2- 1
71 40 Ru 1
1 1
2.46, 126.81, 0.02 6 7a
126
N 1 6
5 3a 2
3 1 2 5
2.51, 129.01, 0.14 2.46, 129.01, 1 2.39, 129.01, 0.03 128 4
3 4
130

2.46, 131.21, 0.03 132
134
2.46, 136.06, 0.03
136
2.51, 136.06, 0.03
138
2.46, 138.26, 0.66
140
142
144
2.55 2.50 2.45 2.40 2.35

Figure S28. 1H NMR spectrum of compound 5d
Acquisition Time (sec) 2.5690 Comment FZ_Grubbs_THQ in CD2Cl2 Date 07 Nov 2019 09:16:48
Date Stamp 07 Nov 2019 09:16:48
File Name C:\Users\Fedor\Desktop\Наброски Статей\2019 Циклические Граббсы\ЯМР\FZ_Grubbs_THQ_002001r Frequency (MHz) 300.13
Nucleus 1H Number of Transients 64 Origin spect Original Points Count 65536
Owner nmr Points Count 262144 Pulse Sequence zg Receiver Gain 114.25
SW(cyclical) (Hz) 25510.20 Solvent DICHLOROMETHANE-d2 Spectrum Offset (Hz) 1350.5919
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
2.47
FZ_Grubbs_THQ_002001r
7.10
4.13
5.36
5.36
18.80
6.99
7.12
1.33
7.53
6.79
6.77
6.96
6.71
3.60
3.34
0.94
3.65
2.27
2.68
7.55
3.29
2.21
3.02
4.50
2.28
2.26
4.22
4.55
0.86 1.06 1.84 4.38 0.92 1.00 1.25
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
Date Stamp 07 Nov 2019 09:16:48
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
FZ_Grubbs_THQ_002001r.esp
7.10
6.99
7.12
7.53
7.26
6.79
7.01
7.53
7.06
6.77
7.07
6.96
6.71
6.69
7.50
7.50
7.28
7.23
7.55
7.55
7.14
7.04
1.00 1.06 7.15 1.84
7.70 7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65 6.60 6.55
Date Stamp 07 Nov 2019 09:16:48
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
2.47
4.13
3.60
3.34
3.65
2.27
2.68
2.63
2.66
2.64
3.29
2.21
3.02
4.50
2.28
4.17
3.03
2.26
3.00
4.22
3.04
3.01
2.72
2.98
4.55
2.70
3.06
2.73
2.23
3.07
2.20
0.85 4.38 0.92 0.91 1.00 17.65 1.25
4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1
Figure S29. 13C NMR spectrum of compound 5d
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_THQ-C13dec [garp-dec] Date 07 Nov 2019 10:10:08
Date Stamp 07 Nov 2019 10:10:08
Nucleus 13C Number of Transients 5434 Origin spect Original Points Count 65536
Owner nmr Points Count 262144 Pulse Sequence zgig Receiver Gain 202.48
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
53.43
53.06
53.79
129.29
20.83
125.97
128.28
52.70
54.15
128.99
138.49
131.18
312.30
57.65 54.86
132.84
148.78
23.98
212.22
49.52
19.22
138.98
136.26
340 320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
Date Stamp 07 Nov 2019 10:10:08
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
129.29
129.22
125.97
128.28
125.88
128.99
128.17
138.49
126.09
126.49
131.18
132.66
132.61
132.84
148.78
138.98
136.26
149 148 147 146 145 144 143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125
Date Stamp 07 Nov 2019 10:10:08
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
53.43
53.06
53.79
20.83
52.70
54.15
54.86
23.98
49.52
57.65
51.51
19.22
58 56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16
Figure S30. NMR DEPT135 spectrum of compound 5d
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_PK-1-dept135 [garp-dec] Date 06 Nov 2019 19:39:44
Date Stamp 06 Nov 2019 19:39:44
Owner nmr Points Count 262144 Pulse Sequence dept135 Receiver Gain 202.48
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
129.29
125.97
126.09
131.17
312.31
20.82
19.15
57.64
49.52
23.98
54.85
380 360 340 320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
Date Stamp 06 Nov 2019 19:39:44
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
129.29
129.21
125.97
126.09
125.87
131.17
128.16
128.98
128.28
126.48
131.5 131.0 130.5 130.0 129.5 129.0 128.5 128.0 127.5 127.0 126.5 126.0 125.5 125.0
Date Stamp 06 Nov 2019 19:39:44
CH3 H3C
1 5 4 1
2 6
3
1
N N 1
5
1 3
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
1 1 5
Cl
41
8
7 8a
N 2 4
1 2 1 3
6 4a 3
5 4
20.82
19.15
51.50
57.64
49.52
23.98
54.85
60 58 56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16
Figure S31. NMR COSY spectrum of compound 5d
Acquisition Time (sec) (0.3408, 0.0710) Comment 5 mm PABBO BB-1H/D Z-GRD Z104275/0345 Date 07 Nov 2019 13:08:40
File Name C:\Users\Fedor\Desktop\Наброски Статей\2019 Циклические Граббсы\ЯМР\FZ_Grubbs_THQ\10\pdata\1\2rr Frequency (MHz) (300.13, 300.13)
Nucleus (1H, 1H) Number of Transients 2 Origin spect Original Points Count (3072, 640)
Owner nmr Points Count (8192, 1024) Pulse Sequence cosygpqf Solvent CD2Cl2
Sweep Width (Hz) (9014.42, 9009.01) Temperature (degree C) 29.947 Title FZ_Grubbs_THQ-COSY
38 43 2 3
FZ_Grubbs_THQ.010.001.2rr.esp CH3 H3C

1 5 4 1
2 6
3 N N 5
1 1 3 1
0.94, 0.92 4
C 4
0 2
1.33, 1.3 H3C 6 2 CH3
1 5 3 1
2.47, 2.09 1
7.1, 2.44 CH3 H3C
3.34, 3.24
3.6, 3.3
2 Cl1 2+ 1
40 Ru 1 6
4.12, 4.12 3 1 1 5
2.98, 2.44 Cl
3.6, 3.56 4 8 41
5.36, 5.35
4.13, 4.26 7 8a
N 2 4
6.68, 6.67 5 1 2 1 3
4.5, 4.47
6.79, 6.76
6 6 4a 3
5 4
7

7.55, 6.96
6.79, 7.23
7.53, 7.52 8
6.96, 7.52 2.47, 7.08
9
10
11
12
13
14
15
16
17
18
19
18.8, 18.79
18 16 14 12 10 8 6 4 2
38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
7.06, 6.67 6.68, 6.67 6.6 H3C 6 2 CH3
1 5 3 1
7.1, 6.7
7.23, 6.76 6.77, 6.76 CH3 H3C
7.53, 6.76 7.28, 6.76 6.79, 6.76 6.7 Cl1 2+ 1
40 Ru 1 6
1 1 5
7.5, 6.76
Cl
6.8 41
8
7 8a
N 2 4
7.55, 6.96 7.11, 6.96 7.09, 6.93 2 1 3
1
7.5, 6.96 7.12, 6.96 6.98, 6.96 6.9
6 4a 3
7.06, 7.05 6.68, 7.05 5 4
7.0

7.01, 6.99
6.71, 7.05
7.13, 7.08 7.1, 7.08 7.1
6.98, 7.11
7.26, 7.23 6.76, 7.23
7.2
7.5, 7.23 7.23, 7.23 6.79, 7.23

7.1, 7.26 7.3
7.4
7.5, 7.49
7.5
7.53, 7.52 7.28, 7.52 7.23, 7.52 6.98, 7.52 6.96, 7.52
7.6
7.7
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7

38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
2.47, 2.09 H3C 6 2 CH3
2.0 1 5 3 1
2.99, 2.24 2.68, 2.21
2.27, 2.27
CH3 H3C
Cl1 2+ 1
40 Ru 1 6
3.02, 2.44 2.98, 2.24 1 1 5
2.62, 2.21 Cl
3.04, 2.62 8 41
2.5
2.98, 2.44 2.47, 2.44
7 8a
N 2 4
1 2 1 3
3.01, 2.62 2.98, 2.62 2.47, 2.62
6 4a 3
2.99, 2.94 3.02, 2.71
5 4

2.47, 2.83
2.65, 2.94 3.0
2.98, 2.94
3.6, 3.3 3.28, 3.32 2.65, 3.06
3.28, 3.24
3.65, 3.3 3.34, 3.32
3.65, 3.56
3.65, 3.65 3.5
4.12, 3.74
3.6, 3.56 3.28, 3.59
3.6, 3.65
4.13, 3.94 3.7, 3.68
4.12, 4.12 4.0

4.13, 4.26 4.04, 4.03
4.5, 4.18
4.5
4.12, 4.5
4.5, 4.47
4.5 4.0 3.5 3.0 2.5
Figure S32. NMR HSQC spectrum of compound 5d
Nucleus (1H, 13C) Number of Transients 4 Origin spect Original Points Count (3072, 540)
Owner nmr Points Count (8192, 1024) Pulse Sequence hsqcetgp Solvent CD2Cl2
Sweep Width (Hz) (9014.42, 34013.61) Temperature (degree C) 29.964 Title FZ_Grubbs_THQ-HSQC [hp-dec]
38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
8
2.5, 18.88 4
C 4
2
2.71, 23.73 16 H3C 6 2 CH3
1 5 3 1
24
CH3 H3C
2.67, 23.73 Cl1 2+ 1
32 40 Ru 1 6
1 1 5
Cl
40 41
3.04, 49.28 8
4.13, 51.04
7 8a
N 2 4
4.55, 57.21 48 2 1 3
1
2.48, 49.28
56 6 4a 3
3.65, 54.56 3.6, 54.56
4.51, 57.65 5 4

64
72
80
88
96
104
112
6.79, 125.92
7.09, 125.92 6.77, 125.92 120
128
6.71, 126.36
7.1, 131.21 6.97, 131.21 136
144
152
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0
38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
124.5 2
7.09, 124.6
H3C 6 2 CH3
125.0 1 5 3 1
CH3 H3C
7.09, 125.92 6.79, 125.92 125.5 Cl1 2+ 1
40 Ru 1 6
126.0 1 1 5
7.12, 126.81
6.77, 125.92 Cl
126.5 8 41
6.71, 126.36
7 8a
N 2 4
7.1, 127.69 127.0 2 1 3
1
7.14, 127.25 127.5 6 4a 3
5 4
7.01, 127.69 128.0

7.53, 128.13
128.5
7.26, 128.57
129.0
7.1, 129.01 6.98, 129.01
129.5
130.0
6.99, 129.89
130.5
7.1, 131.21
131.0
6.97, 131.21 131.5
132.0
132.5
133.0
133.5
134.0
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6
38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
15
4
C 4
2.5, 18.88 2
H3C 6 2 CH3
2.47, 20.21 1 5 3 1
CH3 H3C
2.67, 23.73 20
Cl1 2+ 1
2.71, 23.73 2.25, 23.73
40 Ru 1 6
1 1 5
Cl
25 8 41
7 8a
N 2 4
1 2 1 3
30 6 4a 3
5 4

35
40
45
3.04, 49.28 2.48, 49.28

4.13, 51.04
50
3.34, 54.56
3.6, 54.56 3.29, 54.56
4.55, 57.21 4.22, 57.21 55

3.65, 54.56
4.19, 57.65
4.5 4.0 3.5 3.0 2.5

Figure S33. NMR HMBC spectrum of compound 5d
Owner nmr Points Count (8192, 1024) Pulse Sequence hmbcgplpndqf Solvent CD2Cl2
Sweep Width (Hz) (9014.42, 34013.61) Temperature (degree C) 29.982 Title FZ_Grubbs_THQ-HMBC
38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
7.1, 20.65
7.15, 20.65 0
4
C 4
6.98, 23.73 2.26, 20.65 2
H3C 6 2 CH3
20 1 5 3 1
7.1, 21.97 2.68, 20.65 CH3 H3C
6.97, 57.21 3.65, 57.21 40 Cl1 2+ 1
40 Ru 1 6
1 1 5
6.97, 57.21 3.6, 57.65
60 Cl
8 41
6.68, 54.56
80
7 8a
N 2 4
1 2 1 3
6.7, 125.48 2.47, 121.96 100
18.8, 125.92 7.52, 125.92 6 4a 3
2.47, 129.01
120 5 4

18.81, 132.53 7.52, 132.53 140
2.47, 138.26
18.81, 148.39 6.97, 148.39 160
180
200
18.8, 212.26 4.12, 212.26 220
240
260
280
300
6.77, 312.25 320
18 16 14 12 10 8 6 4 2
38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
18.81, 127.25 C
125 4 2 4
18.81, 132.53 18.8, 125.92 H3C 6 2 CH3
1 5 3 1
130
CH3 H3C
18.8, 131.21 135 Cl1 2+ 1
40 Ru 1 6
1 1 5
140 Cl
18.81, 148.39 18.79, 148.39 8 41
145
7 8a
N 2 4
1 2 1 3
150
6 4a 3
155 5 4

160
165
170
175
180
185
190
195
200
205
18.8, 212.26
210
18.825 18.820 18.815 18.810 18.805 18.800 18.795 18.790 18.785 18.780 18.775
38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
15
4
C 4
2
H3C 6 2 CH3
2.68, 20.65 2.26, 20.65 1 5 3 1
20 CH3 H3C
2.72, 20.65 2.3, 20.65
Cl1 2+ 1
40 Ru 1 6
1 1 5
2.44, 23.73 25
Cl
8 41
7 8a
N 2 4
1 2 1 3
30
6 4a 3
5 4

35
40
2.23, 49.28 45
3.29, 49.28 2.71, 49.28 2.25, 49.28
4.16, 51.04
4.09, 51.48
50
3.34, 49.28 2.99, 54.56
3.07, 54.56 2.43, 55
2.99, 57.65 55
3.65, 57.21 3.07, 57.21

3.6, 57.65 60
4.0 3.5 3.0 2.5

38 43 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
2.47, 125.92 125
4
C 4
2
H3C 6 2 CH3
126 1 5 3 1
2.47, 127.69 CH3 H3C
2.21, 128.13 127
Cl1 2+ 1
40 Ru 1 6
2.47, 129.01 128 1 1 5
Cl
129 8 41
2.47, 130.33
7 8a
N 2 4
130 1 2 1 3
131 6 4a 3
3.28, 132.53 2.64, 132.53 2.21, 132.53
3.65, 132.53 2.99, 132.53 2.67, 132.53 2.27, 132.53 5 4

132
3.07, 132.09
3.6, 132.53 3.34, 132.53 2.73, 132.53 2.47, 132.53 133
134
135
2.47, 134.73
136
137
2.47, 136.94
138
2.47, 138.26
139
2.47, 139.58 140
141
142
2.47, 141.78
143
3.5 3.0 2.5
38 43 2 3

1 5 4 1
2 6
3 N N 5
208 1 1 3 1
4
C 4
2
4.12, 212.26 H3C 6 2 CH3
216 1 5 3 1
CH3 H3C
224 Cl1 2+ 1
40 Ru 1 6
1 1 5
232
Cl
8 41
7 8a
N 2 4
240 1 2 1 3
6 4a 3
248 5 4

256
264
272
280
288
296
304
6.77, 312.25
312
7.0 6.5 6.0 5.5 5.0 4.5 4.0

Figure S34. 1H NMR spectrum of compound 5e
Acquisition Time (sec) 2.5690 Comment H1 Date 02 Oct 2018 14:56:00
Date Stamp 02 Oct 2018 14:56:00
File Name C:\Users\Fedor\Desktop\Наброски Статей\Кирилл Статья по Катализаторам Граббса\ЯМР Граббс\ЯМР Граббс от Ромы\Grubbs_12-K10 (Морфолиновый)_003001r
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
2.44
Grubbs_12-K10 (Морфолиновый)_003001r
4.12
7.10
2.53
18.95
7.09
5.36
5.36
6.68
7.25
7.49
6.65
7.06
3.23
2.02
3.54
3.21
3.22
2.05
3.56
2.06
2.04
2.02
7.52
0.96 1.15 1.00 4.17 2.41
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1
Date Stamp 02 Oct 2018 14:56:00
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
7.10
7.09
6.68
7.25
7.49
7.06
6.65
7.47
7.27
7.23
7.52
1.32 1.15 5.01 1.00
7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65 6.60 6.55
Date Stamp 02 Oct 2018 14:56:00
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
2.44
4.12
2.53
3.23
2.02
3.54
3.21
3.22
2.05
3.56
2.06
3.56
3.06
2.04
2.02
3.57
2.00
3.05
2.07
3.53
3.03
3.58
3.07
3.19
3.06
3.09
3.20
3.60
3.24
3.18
3.10
3.17
3.61
2.30
2.33
5.89 2.09 4.17 18.40 2.41
4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0
Figure S35. 13C NMR spectrum of compound 5e
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_12-K10-C13dec [hp-dec] Date 02 Oct 2018 12:50:08
Date Stamp 02 Oct 2018 12:50:08
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
53.58
53.22
53.94
129.32
53.06
62.73
52.86
54.30
20.80
129.06
131.51
128.07
122.18
316.18
60.62
138.74
151.27
210.71
51.64
139.16
19.78
19.40
18.50
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
Date Stamp 02 Oct 2018 12:50:08
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
129.32
129.06
131.51
128.07
122.18
130.82
138.74
151.27
139.16
136.23
152 150 148 146 144 142 140 138 136 134 132 130 128 126 124 122 120
Date Stamp 02 Oct 2018 12:50:08
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
53.94
53.58
Grubbs_12-K10 (Морфолиновый)_013001r 53.22 53.06
62.73
52.86
54.30
20.80
60.62
51.64
19.78
19.40
18.50
64 62 60 58 56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16
Figure S36. NMR DEPT135 spectrum of compound 5e
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_12-K10-dept135 [hp-dec] Date 02 Oct 2018 15:00:16
Date Stamp 02 Oct 2018 15:00:16
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
129.32
20.80
131.51
128.07
129.06
122.18
316.18
19.01
51.49
60.62
53.06
62.73
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
Date Stamp 02 Oct 2018 15:00:16
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
129.32
131.51
128.07
129.06
122.18
134 133 132 131 130 129 128 127 126 125 124 123 122 121 120
Date Stamp 02 Oct 2018 15:00:16
CH3 H3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
6 N 2 4
4 1 3
3
O
1 2
20.80
19.01
51.49
60.62
62.73
53.06
64 62 60 58 56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16 14
Figure S37. NMR COSY spectrum of compound 5e
Acquisition Time (sec) (0.3408, 0.0074) Comment 5 mm PABBO BB-1H/D Z-GRD Z104275/0345 Date 02 Oct 2018 19:52:12
File Name C:\Users\Fedor\Desktop\ЯМР Граббс Морфолин\FZ_Grubbs_12-K10\114\pdata\1\2rr Frequency (MHz) (300.13, 75.48)
Owner nmr Points Count (8192, 2048) Pulse Sequence hsqcedetgp Solvent CD2Cl2
Sweep Width (Hz) (9014.42, 34013.61) Temperature (degree C) 30.020 Title FZ_Grubbs_12-K10-edited-HSQC [hp-dec]
Formula C H Cl N ORu FW 667.6730
33 41 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
-40
4
C 4
2
-20 H3C 6 2 CH3
1 5 3 1
CH3 H3C
0
Cl1 2+ 1
20 22 Ru 1 6
1 1 5
Cl
40 16 5
6 N 2 4
60 4 1 3
3
80 O
1 2

100
120
140
160
180
200
220
240
260
280
300
18 16 14 12 10 8 6 4 2
33 41 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
119 2
H3C 6 2 CH3
1 5 3 1
120 CH3 H3C
121 Cl1 2+ 1
22 Ru 1 6
1 1 5
122 Cl
16 5
123
6 N 2 4
4 1 3
124
3
O
125 1 2

126
127
128
129
130
131
132
133
134
135
136
137
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5
33 41 2 3
N N
C
H3C CH3
20
CH3 H3C
Cl 2+
Ru
25
Cl
N
30
O
35

40
45
50
55
60
65
4.0 3.5 3.0 2.5 2.0

Figure S38. NMR HSQC spectrum of compound 5e
Sweep Width (Hz) (9014.42, 34013.61) Temperature (degree C) 29.873 Title FZ_Grubbs_12-K10-HMBC
33 41 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
-20 2
H3C 6 2 CH3
1 5 3 1
0
CH3 H3C
20 Cl1 2+ 1
22 Ru 1 6
1 1 5
40 Cl
16 5
60 6 N 2 4
4 1 3
80 3
O
100 1 2

120
140
160
180
200
220
240
260
280
300
320
22 20 18 16 14 12 10 8 6 4 2 0
33 41 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
120 2
H3C 6 2 CH3
1 5 3 1
125
CH3 H3C
130 Cl1 2+ 1
22 Ru 1 6
135 1 1 5
Cl
140 16 5
6 N 2 4
145 4 1 3
3
150 O
1 2

155
160
165
170
175
180
185
190
195
200
205
210
215
19.20 19.15 19.10 19.05 19.00 18.95 18.90 18.85 18.80 18.75 18.70 18.65 18.60
33 41 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
4
C 4
2
20 H3C 6 2 CH3
1 5 3 1
CH3 H3C
40 Cl1 2+ 1
22 Ru 1 6
1 1 5
Cl
16 5
60
6 N 2 4
4 1 3
3
80 O
1 2

100
120
140
160
180
200
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5
Figure 39. NMR HMBC spectrum of compound 5e
Acquisition Time (sec) (0.3408, 0.0642) Comment 5 mm PABBO BB-1H/D Z-GRD Z104275/0345
Date 02 Oct 2018 18:30:04
File Name C:\Users\Fedor\Desktop\Наброски Статей\Кирилл Статья по Катализаторам Граббса\ЯМР Граббс\ЯМР Граббс от Ромы\Grubbs_12-K10 (Морфолиновый)\11\pdata\1\2rr
Frequency (MHz) (300.13, 300.13) Nucleus (1H, 1H) Number of Transients 1
Origin spect Original Points Count (3072, 578) Owner nmr
Points Count (8192, 2048) Pulse Sequence cosygpqf Solvent CD2Cl2
Sweep Width (Hz) (9014.42, 9009.01) Temperature (degree C) 29.656 Title FZ_Grubbs_12-K10-COSY
33 41 2 3
Grubbs_12-K10 (Морфолиновый).011.001.2rr.esp CH3 H3C

1 5 4 1
2 6
3 N N 5
0
1 1 3 1
4
C 4
2
H3C 6 2 CH3
1 5 3 1
2 CH3 H3C
Cl1 2+ 1
22 Ru 1 6
1 1 5
4 Cl
16 5
6 N 2 4
6 4 1 3
3
O
2

1
8
10
12
14
16
18
18 16 14 12 10 8 6 4 2
Date 02 Oct 2018 18:30:04
33 41 2 3

1 5 4 1
2 6
3 N N 5
1 1 3 1
2.0 4
C 4
2
H3C 6 2 CH3
1 5 3 1
2.5 CH3 H3C
Cl1 2+ 1
22 Ru 1 6
3.0 1 1 5
Cl
16 5
3.5 6 N 2 4
4 1 3
3
4.0 O
2

1
4.5
5.0
5.5
6.0
6.5
7.0
7.5
7.5 7.0 6.5

Date 02 Oct 2018 18:30:04
33 41 2 3

1 5 4 1
2 6
3 N N 5
1.5
1 1 3 1
4
C 4
2
H3C 6 2 CH3
2.0 1 5 3 1
CH3 H3C
Cl1 2+ 1
2.5
22 Ru 1 6
1 1 5
Cl
3.0 16 5
6 N 2 4
4 1 3
3.5
3
O
2

1
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
3.5 3.0 2.5 2.0

Figure S40. 1H NMR spectrum of compound 5f
Acquisition Time (sec) 2.5690 Comment FZ_Grubbs_FZ7712 in CD2Cl2 Date 20 Aug 2019 19:05:36
Date Stamp 20 Aug 2019 19:05:36
File Name C:\Users\Fedor\Desktop\2019 ЯМР Рома Август Граббсы и Перенос Ароматичности\FZ_Grubbs_FZ7712_001001r
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
7.08
FZ_Grubbs_FZ7712_001001r
2.43
4.11
5.36
2.14
2.51
18.79
4.35
2.25
7.06
6.73
7.23
7.52
6.70
2.83
2.86
7.54
0.95 1.05 1.00 4.00 2.45 28.01
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
Date Stamp 20 Aug 2019 19:05:36
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
7.08
7.06
6.73
7.23
7.52
6.70
7.50
7.25
7.20
7.54
1.09 1.05 4.85 1.00
7.65 7.60 7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65 6.60
Date Stamp 20 Aug 2019 19:05:36
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
2.43
4.11
2.14
2.51
2.46
4.35
2.25
2.29
2.20
2.37
2.83
2.32
2.79
2.86
2.04 4.00 2.45 28.01
4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8
Figure 41. 13C NMR spectrum of compound 5f
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_FZ7712-C13dec [hp-dec] Date 20 Aug 2019 19:46:08
Date Stamp 20 Aug 2019 19:46:08
File Name C:\Users\Fedor\Desktop\2019 ЯМР Рома Август Граббсы и Перенос Ароматичности\FZ_Grubbs_FZ7712_013001r Frequency (MHz) 75.47
Owner nmr Points Count 262144 Pulse Sequence zgpg Receiver Gain 202.48
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
53.41
129.29
53.77
53.05
52.69
20.79
128.23
128.84
54.13
131.33
51.02
49.43
138.50
124.75
313.77
132.25
149.51
45.57
211.82
56.77
138.89
19.25
18.92
20.06
18.04
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
Date Stamp 20 Aug 2019 19:46:08
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
129.29
128.23
128.84
131.33
138.50
124.75
132.25
149.51
138.89
138.23
135.19
135.57
150 149 148 147 146 145 144 143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123
Date Stamp 20 Aug 2019 19:46:08
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
53.41
53.77
53.05 52.69
20.79
54.13
51.02
49.43
51.39
45.57
56.77
19.25
20.37
17.83
62 60 58 56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16 14 12
Figure 42. NMR DEPT135 spectrum of compound 5f
Acquisition Time (sec) 1.1010 Comment FZ_Grubbs_FZ7712-dept135 [hp-dec] Date 20 Aug 2019 23:13:04
Date Stamp 20 Aug 2019 23:13:04
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
129.29
131.33
128.24
128.85
20.79
124.75
313.78
45.54
53.62
56.83
51.54
49.44
51.02
320 300 280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
Date Stamp 20 Aug 2019 23:13:04
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
129.29
131.33
128.24
128.85
124.75
133.0 132.5 132.0 131.5 131.0 130.5 130.0 129.5 129.0 128.5 128.0 127.5 127.0 126.5 126.0 125.5 125.0 124.5 124.0 123.5 123.0
Date Stamp 20 Aug 2019 23:13:04
CH 3 H 3C
1 5 4 1
2 6
3 N N 5
1 1 3 1
C
4 2 4
H 3C 6 2 CH 3
1 5 3 1
CH 3 H 3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
Cl
17 2
3 N 2 4
1 1 3
6
N
4 5
H 3C
1
20.79
45.54
53.62
56.83
51.54
49.44
51.02
56 54 52 50 48 46 44 42 40 38 36 34 32 30 28 26 24 22 20 18 16
Figure S43. NMR COSY spectrum of compound 5f
Acquisition Time (sec) (0.3408, 0.0710) Comment 5 mm PABBO BB-1H/D Z-GRD Z104275/0345 Date 21 Aug 2019 10:53:18
File Name C:\Users\Fedor\Desktop\2019 ЯМР Рома Август Граббсы и Перенос Ароматичности\FZ_Grubbs_FZ7712\11\pdata\1\2rr Frequency (MHz) (300.13, 300.13)
Sweep Width (Hz) (9014.42, 9009.01) Temperature (degree C) 29.998 Title FZ_Grubbs_FZ7712-COSY
34 44 2 4

1 5 4 1
2 6
3 N N 5
0 1 1 3 1
4
C 4
2.32, 2.09 2
1 H3C 6 2 CH3
7.08, 2.42 2.43, 2.42 1 5 3 1
3.44, 3.41 2 CH3 H3C
3.84, 3.82 Cl1 2+ 1
4.11, 4.09 3
23 Ru 1 6
5.36, 5.35 1 1 5
4 Cl
17 2
7.23, 4.32 4.34, 4.32 5 3 N 2 4
6.73, 6.7 1 1 3
6 6
N
7.87, 7.87 7 4 5
6.7, 6.7 H3C

6.7, 7.23 2.43, 7.05 1
6.73, 7.23 8
9
10.46, 10.45
10
11
12
13
14
4.1, 14.47 15
16
17
7.07, 17.44 18
19
18 16 14 12 10 8 6 4 2
34 44 2 4

1 5 4 1
2 6
3 N N 5
1 1 3 1
7.08, 2.42
4
C 4
2
H3C 6 2 CH3
2.5 1 5 3 1
CH3 H3C
Cl1 2+ 1
3.0 23 Ru 1 6
1 1 5
Cl
17 2
3.5
3 N 2 4
1 1 3
6
7.23, 4.32 7.05, 4.32 4.0 N
4 5
H3C

1
7.07, 4.35 4.5
5.0
5.5
6.0
7.49, 6.7 7.2, 6.7
7.52, 6.7 7.25, 6.7 6.73, 6.7
6.82, 6.79 6.5
7.49, 7.05 7.49, 7.2 7.08, 7.05 7.04, 7.05

7.23, 7.2 6.7, 6.7
6.73, 7.23
7.0
7.49, 7.49
7.55, 7.05 7.2, 7.49 7.05, 7.49 6.73, 7.49
7.55, 7.2 6.7, 7.23
7.25, 7.23 7.5
7.52, 7.49 7.25, 7.49 7.08, 7.49 6.7, 7.49
7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5
34 44 2 4

1 5 4 1
2 6
3 N N 5
1 1 3 1
2.79, 2.18 2.25, 2.09
2.12, 2.27 4
C 4
2.82, 2.21 2.26, 2.24 2
2.0 H3C 6 2 CH3
2.46, 2.44 1 5 3 1
2.83, 2.21 2.64, 2.62 2.29, 2.12 2.14, 2.12 CH3 H3C
2.82, 2.33 2.79, 2.33
2.43, 2.42 2.37, 2.36 2.14, 2.8 2.5 Cl1 2+ 1
2.58, 2.56 23 Ru 1 6
1 1 5
2.86, 2.8 2.79, 2.8 2.43, 2.53 2.24, 2.8 2.1, 2.77 Cl
3.0 17 2
2.83, 2.83 2.28, 2.86
3 N 2 4
1 1 3
3.5
6
N
4 5
H3C

4.0 1
4.5
5.0
5.5
6.0
6.5
7.0
2.43, 7.05
7.5
2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9
Figure S44. NMR HSQC spectrum of compound 5f
Date 21 Aug 2019 10:54:10 File Name C:\Users\Fedor\Desktop\2019 ЯМР Рома Август Граббсы и Перенос Ароматичности\FZ_Grubbs_FZ7712\113\pdata\1\2rr
Frequency (MHz) (300.13, 75.48) Nucleus (1H, 13C) Number of Transients 4
Points Count (8192, 1024) Pulse Sequence hsqcetgp Solvent CD2Cl2
Sweep Width (Hz) (9014.42, 34013.61) Temperature (degree C) 29.971 Title FZ_Grubbs_FZ7712-HSQC [hp-dec]
34 44 2 4

1 5 4 1
2 6
3 N N 5
1 1 3 1
2.43, 20.21 0
4
C 4
2
H3C 6 2 CH3
2.29, 49.28 20 1 5 3 1
4.11, 51.04 CH3 H3C
40
Cl1 2+ 1
23 Ru 1 6
5.36, 53.24 60 1 1 5
4.34, 56.77 Cl
17 2
80
3 N 2 4
1 1 3
6.73, 124.6 100
6
7.23, 128.57 N
120 4 5
H3C

1
7.08, 129.01 7.08, 131.21 140
160
180
200
220
240
260
280
300
18.8, 314.02 320
18 16 14 12 10 8 6 4 2
34 44 2 4

1 5 4 1
2 6
3 N N 5
1 1 3 1
120
4
C 4
2
121 H3C 6 2 CH3
1 5 3 1
122 CH3 H3C
6.71, 123.72
123 Cl1 2+ 1
6.73, 124.6
23 Ru 1 6
1 1 5
124 Cl
17 2
125
3 N 2 4
126 1 1 3
6
7.52, 128.13 127 N
4 5
H3C

7.52, 129.01 128 1
7.23, 128.57 129
7.08, 129.01
130
7.08, 129.89
7.06, 130.33 131
7.08, 131.21
132
133
134
135
136
137
138
139
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6
34 44 2 4

1 5 4 1
2 6
3 N N 5
15 1 1 3 1
4
C 4
2
2.43, 20.21 H3C 6 2 CH3
1 5 3 1
2.43, 21.53
20 CH3 H3C
Cl1 2+ 1
23 Ru 1 6
1 1 5
25 Cl
17 2
3 N 2 4
1 1 3
30 6
N
4 5
H3C

1
35
40
2.14, 45.31
45
2.15, 49.28
4.11, 51.04 2.84, 50.6
2.29, 49.28 50
2.25, 50.6
55
4.34, 56.77
4.0 3.5 3.0 2.5 2.0

Figure S45. NMR HMBC spectrum of compound 5f
Sweep Width (Hz) (9014.42, 34013.61) Temperature (degree C) 29.998 Title FZ_Grubbs_FZ7712-HMBC
34 44 2 4

1 5 4 1
2 6
3 N N 5
1 1 3 1
7.08, 20.65 2.64, 20.65
4
C 4
2
20 H3C 6 2 CH3
2.14, 49.28 1 5 3 1
7.07, 21.97
3.84, 52.36
40
CH3 H3C
Cl1 2+ 1
4.34, 50.6 60
23 Ru 1 6
1 1 5
Cl
80 17 2
3 N 2 4
1 1 3
7.08, 129.01 100
18.79, 124.6 7.51, 124.6 6
7.53, 132.09 2.43, 129.01 N
120 4 5
3.84, 140.9 H3C

1
18.79, 132.09 7.51, 132.09 140
6.7, 132.09 2.43, 138.26
18.78, 149.27 160
180
200
18.79, 211.82 4.11, 211.82 220
240
260
280
6.7, 313.57 300
6.72, 313.57 320
18 16 14 12 10 8 6 4 2
34 44 2 4

1 5 4 1
2 6
3 N N 5
1 1 3 1
18.79, 124.6 120 4
C 4
2
H3C 6 2 CH3
125 1 5 3 1
18.79, 132.09 CH3 H3C
130
Cl1 2+ 1
23 Ru 1 6
135 1 1 5
Cl
140 17 2
18.8, 149.27 18.78, 149.27
3 N 2 4
145 1 1 3
6
150 N
4 5
155
H3C

1
160
165
170
175
180
185
190
195
200
205
210
18.79, 211.82 215

18.83 18.82 18.81 18.80 18.79 18.78 18.77 18.76 18.75 18.74 18.73
34 44 2 4

1 5 4 1
2 6
3 N N 5
1 1 3 1
120
4
C 4
2
7.53, 124.6
H3C 6 2 CH3
122 1 5 3 1
7.51, 124.6 CH3 H3C
124 Cl1 2+ 1
23 Ru 1 6
126 1 1 5
6.71, 128.13 Cl
7.08, 129.01 17 2
128
3 N 2 4
7.22, 131.21 1 1 3
7.51, 132.09 130
6
N
132 4 5
H3C

7.53, 132.09 6.7, 132.09 1
134
136
138
140
142
144
146
7.22, 149.27 7.06, 149.27

148
7.23, 149.27 150
152
154
7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7
34 44 2 4

1 5 4 1
2 6
3 N N 5
120 1 1 3 1
4
C 4
2
4.34, 131.42
125 H3C 6 2 CH3
1 5 3 1
130 CH3 H3C
Cl1 2+ 1
135
23 Ru 1 6
1 1 5
140 Cl
17 2
4.34, 149.13 145 3 N 2 4
1 1 3
150
6
N
155 4 5
H3C

160 1
165
170
175
180
185
190
195
200
205
4.11, 211.82
210
215
4.40 4.35 4.30 4.25 4.20 4.15 4.10 4.05

34 44 2 4

1 5 4 1
2 6
3 N N 5
1 1 3 1
2.21, 20.29 4
C 4
16 2
H3C 6 2 CH3
1 5 3 1
2.64, 20.65 24 CH3 H3C
Cl1 2+ 1
32 23 Ru 1 6
1 1 5
Cl
40 17 2
2.14, 49.28
3 N 2 4
2.26, 54.88 48 1 1 3
6
56 N
4 5
H3C

64 1
72
80
88
96
104
112
120
2.43, 129.01 2.37, 129.89
2.46, 135.17 128
2.37, 141.27
136
2.43, 138.26
2.65 2.60 2.55 2.50 2.45 2.40 2.35 2.30 2.25 2.20 2.15 2.10
For Table 4 Line 1
Acquisition Time (sec) 1.9818 Comment single_pulse Date 28 Jul 1990 07:49:06
Date Stamp 07 Oct 2019 13:51:59 File Name G:\TABLE 4\FZ7934-1 TABLE 4 100 TO 0.JDF
Frequency (MHz) 600.17 Nucleus 1H Number of Transients 8 Origin ECA 600
Original Points Count 32768 Owner delta Points Count 32768 Pulse Sequence single_pulse.ex2
0.00
FZ7934-1 TABLE 4 100 TO 0.JDF
7.25
7.33
7.40
5.77
5.74
5.25
7.42
5.24
6.70
6.72
6.73
6.75
1.53
7.24
0.01
1.34 0.96 1.00 1.00
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
For Table 4 Line 2
7.32

7.40
5.76
5.73
0.00
5.25
7.41
5.23
7.31
7.24
6.71
6.70
1.52
6.74
7.11
7.51
7.52
7.24
5.40
4.30 0.21 0.95 1.00 0.99
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
For Table 4 Line 3
Acquisition Time (sec) 1.9818 Comment single_pulse
Date 28 Jul 1990 07:38:16
7.25
0.00
7.32
7.40
7.42
5.76
5.25
1.53
5.73
5.23
6.70
6.72
6.73
6.74
7.24
7.11
7.51
7.52
0.01
0.15 2.10 0.12 0.96 1.00 0.99
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
For Table 4 Line 4
0.00
7.11
7.32
7.40
7.51
7.24
5.76
7.52
5.73
5.25
5.23
1.52
6.71
6.70
6.72
6.74
7.24
3.77 0.92 0.96 1.00 1.00
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
For Table 4 Line 5
0.00
7.11
7.36
7.25
7.51
7.53
1.54
7.37
7.25
-0.01
7.40
0.01
5.77
5.74
5.25
5.24
0.04
7.15
6.72
6.70
6.75
6.73
1.25
2.35 12.86 0.97 1.00 0.99
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
For Table 4 Line 6
7.25
0.00
7.32
7.40
1.53
7.42
5.25
5.23
5.76
5.74
7.11
6.70
6.73
6.72
7.51
6.74
7.52
7.24
0.662.60 0.38 0.97 1.00 1.00
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
For Table 4 Line 7
Date 04 Aug 1990 06:09:08
5.28
7.32
7.40
0.00
7.41
5.25
5.76
5.73
5.23
7.31
7.25
7.24
6.70
6.71
6.72
6.74
1.52
7.11
7.51
7.52
1.25
2.26
4.16 0.14 0.96 1.00 0.99
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
For Table 4 Line 8
Acquisition Time (sec) 1.9818 Comment single_pulse Date 01 Aug 1990 06:15:51
0.00
7.26
1.54
7.33
7.12
7.41
5.77
5.25
5.74
5.24
7.42
7.51
7.53
6.70
6.72
6.73
6.75
5.30
7.24
1.25 3.16 0.69 0.97 1.00 0.99
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
For Table 4 Line 9
0.00
7.32
7.40
5.28
7.42
5.25
7.11
5.77
7.24
1.53
5.23
5.74
7.51
6.70
6.71
7.52
6.73
6.74
7.24
2.16
2.26
2.80 0.45 0.98 1.00 1.01
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
For Table 4 Line 10
7.11
0.00
7.36
7.51
7.52
7.25
7.35
7.37
1.53
3.94 1.99
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
For Table 4 Line 11
7.11
7.36
7.51
0.00
7.52
7.26 7.34
7.37
7.24
1.52
3.95 2.00
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
For Table 4 Line 12
FZ7958-1 TABLE 4 61 TO 39.JDF7.11
7.36
7.51
7.32
7.40
7.52
5.25
7.26
5.76
0.00
5.23
5.73
7.23 7.25
0.07
1.51
6.69
6.71
6.72
6.74
5.27
2.458.80 1.25 0.97 1.01 1.00
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
For Table 5 Line 1 (0.1 mol%)
4.12
2.43
0.00
5.65
7.72
7.26
7.73
7.33
3.81
3.80
5.15
5.13
7.70
1.57
5.65
5.59
5.61
7.71 10.01 7.58 3.96 12.20 4.00 12.14
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Date 28 Jul 1990 07:06:08
4.12
2.43
5.65
0.00
7.71
7.33
7.73
7.31
7.26
1.58
30.08 30.95 29.60 3.58 60.90 4.00 47.90
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
4.12
2.43
0.00
5.65
7.26
7.72
7.73
7.33
3.81
3.80
5.15
7.70
1.92
5.13
4.15
2.46
4.08
19.91 20.54 19.61 4.01 38.65 4.00 30.81
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
4.12
2.43
0.00
5.65
7.26
7.73
7.72
7.33
0.07
4.13
5.66
5.65
3.80
3.81
4.16
4.09
4.10
5.15
2.40
7.70
3.85
2.46
1.26
5.13
3.78
5.13
3.74
2.47
2.41
1.34
30.99 31.76 29.87 3.20 63.14 4.00 49.63
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
4.12
2.43
5.65
0.00
7.71
7.73
7.33
7.31
7.26
1.90 1.93 1.89 4.01 3.00
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
Date 28 Jul 1990 07:11:31
4.12
2.43
0.00
5.65
7.26
7.72
7.73
7.33
1.58
44.08 44.68 42.44 4.13 88.00 4.00 68.65 13.61
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Date 29 Aug 1990 06:47:40
Date Stamp 08 Nov 2019 12:04:43 File Name G:\TABLE 5\FZ8106-1 TABLE 5 85 TO 15.JDF
2.42
-0.01
3.79
3.78
7.25
5.14
7.70
7.69
4.11
5.12
7.29
5.11
1.57
5.56 5.57
5.59
5.62
5.60
5.64
7.71
7.31
1.82 2.42 1.84 3.36 0.59 3.49 3.00 0.52
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Date 22 Aug 1990 05:38:53
0.00
4.12
2.43
7.26
3.81
3.80
5.65
7.71
5.15
7.70
7.33 7.30
5.13
7.73
5.13
1.57
5.59
5.62
5.60
5.63
1.95 1.94 2.02 2.31 1.81 2.23 3.00
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
Date 29 Aug 1990 07:03:29
2.43
4.12
0.00
3.80
3.81
7.71
7.27
5.65
7.70
5.15
5.16
5.13
7.31
5.13
7.73
7.31
7.33
0.07
5.58 5.59
5.60
5.62
5.63
1.78
4.00
1.34
1.26
1.86 2.33 1.87 2.33 1.66 2.42 3.00
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Date 22 Aug 1990 05:28:37
4.12
0.00
2.43
5.65
7.26
7.72
7.73
7.31
7.33
3.80
1.58
3.81
5.15
7.70
5.15
5.13
5.13
5.66
5.65
5.59
1.98 1.99 0.48 1.14 2.88 3.00 0.44
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
0.00
4.12
2.43
7.26
5.65
7.72
7.73
7.33
4.11
0.01
4.13
1.89 1.82 1.82 0.35 3.80 0.37 3.00
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Date 22 Aug 1990 05:33:45
4.12
0.00
2.43
5.65
3.80
7.26
3.81
7.71
5.15
7.70
7.73
7.30
5.16
5.13
7.33
5.13
5.61
5.59
5.62
5.63
4.11
5.66
1.59
1.87 1.91 1.06 2.00 2.01 2.01 3.00
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
For Table 6 Line 1
10.11.2020 19:46:09
Acquisition Time (sec) 1.9818 Comment single_pulse Date 10 Nov 2020 10:35:25
Date Stamp 10 Nov 2020 09:49:31 File Name C:\USERS\ALEXA\DOWNLOADS\FZ9243-1.JDF
Original Points Count 32768 Owner CKP Points Count 32768 Pulse Sequence single_pulse.ex2
Receiver Gain 32.00 Solvent DMSO-d6 Spectrum Offset (Hz) 5426.2700 Sweep Width (Hz) 16534.39
2.02
FZ9243-1.JDF
2.07 2.03
4.64
4.63
3.35
7.27
4.54
4.53
5.70
7.35
2.51
4.70
7.46
7.61
7.47
7.62
5.68 5.70
5.73 5.71
0.00
6.38
3.33
5.84
6.67
6.36
6.69
6.37
6.39
2.09
6.35
2.00
6.37
4.80
4.80
2.13
1.91
2.35
6.68
4.05
2.00
16.66 27.23 10.01 8.77 21.06 3.08 19.79 100.56
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
10.11.2020 19:47:16
FZ9243-1.JDF
7.27
7.35
7.46
7.39
7.61
7.47
7.62
7.28
7.37
7.33
6.38
7.40
7.29
6.67
6.36
6.69
6.37
6.39
6.35
7.32
7.42
6.68
7.33
16.66 18.24 37.37 27.23 10.01 8.77
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4
10.11.2020 19:47:35
FZ9243-1.JDF
4.64
4.63
4.54
4.53
5.70
4.70
4.69
5.70
5.71
5.84
4.80
4.80
4.79
4.66
4.61
5.73
5.68
5.80
5.78
8.57 21.06 3.08 18.31 48.10 19.79
5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5
10.11.2020 19:47:53
2.02
FZ9243-1.JDF
2.03
2.07
3.35
2.51
3.33
2.09
2.00
2.05
2.13
1.91
2.35
2.00
100.56
3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8
For Table 6 Line 2
10.11.2020 19:52:46
3.35
FZ9244-1.JDF
2.07
2.03
2.50
3.33
7.26
2.02
4.54
7.35
4.53
4.69
7.39
4.69
7.46
7.61
7.62
0.00
6.38
6.36
6.67
5.84
6.69
6.37
6.39
4.64
6.35
2.34
5.70
4.80
2.00
18.02 27.24 9.99 9.52 1.72 1.92 16.76 5.48
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
10.11.2020 19:53:17
FZ9244-1.JDF
7.26
7.35
7.39
7.46
7.61
7.47
7.62
7.27
7.33
7.40
7.37
6.38
6.36
7.29
6.67
6.69
6.37
6.39
6.35
7.40
18.02 19.83 38.07 27.24 9.99 9.52
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4
10.11.2020 19:58:01
FZ9244-1.JDF
4.54
4.53
4.69
4.69
5.84
4.64
4.63
5.70
4.80
4.79
7.45 0.54 1.72 1.92 19.77 3.58 16.76
5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5
10.11.2020 19:58:19
3.35
FZ9244-1.JDF
2.07
2.03
2.50
3.33
2.02
2.34
2.00
27.43 5.48
3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9
For Table 6 Line 3
10.11.2020 18:43:27
Date Stamp 06 Nov 2020 11:55:38 File Name C:\Users\User\Desktop\FZ9237-1.jdf Frequency (MHz) 600.17
Nucleus 1H Number of Transients 8 Origin ECA 600 Original Points Count 32768 Owner CKP
Points Count 32768 Pulse Sequence single_pulse.ex2 Receiver Gain 40.00 Solvent DMSO-d6
Spectrum Offset (Hz) 5425.7656 Sweep Width (Hz) 16534.39
2.07
FZ9237-1.ESP
2.03
3.35
7.27
2.02
2.51
7.35
7.39
4.69
4.69
4.53
4.54
7.61
4.68
2.50
7.62
7.47
7.62
6.39 6.38
6.36
0.00
6.67
2.51
3.33
2.50
6.69
5.84
4.63
5.84
6.35
5.85
5.70
4.80
4.80
5.69
5.71
5.78
5.80
19.22 28.97 10.00 9.35 2.01 1.85 13.81 33.25 6.21
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
10.11.2020 18:43:44
FZ9237-1.ESP
7.27
7.35
7.39
7.61
7.46
7.62 7.62
7.47
7.60
7.28
7.37
7.47
6.38
7.34
7.40
7.36
7.29
6.36
6.67
6.69
6.39
6.37
6.35
7.29
19.22 19.68 20.15 19.15 28.97 10.00 9.35
7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4
10.11.2020 18:44:03
FZ9237-1.ESP
4.69
4.69
4.53
4.70
4.54
4.68
5.84
4.63
4.64
5.84
5.85
5.70
4.80
4.79
4.80
4.79
5.70
5.69
5.70
5.71
5.71
5.69
5.78
5.80
5.79
5.68
5.82 0.80 2.01 1.85 19.17 4.06 13.81
5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5
10.11.2020 18:44:22
2.07
FZ9237-1.ESP
2.03
3.35
2.02
2.51
2.50
2.51
2.51
3.33
2.50
33.25 26.66 6.21
3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9
For Table 6 Line 4
10.11.2020 19:18:37
2.03
2.07
FZ9242-1.JDF
2.02
3.36
7.27
4.53
4.54
7.35
4.70
4.69
2.51
7.46
7.47
7.61
7.62
6.38
4.63
5.84
6.36
6.67
3.33
0.00
6.69
5.84
6.37
6.35
6.39
5.70
2.01
5.71
5.70
2.00
4.80
15.48 26.23 10.05 3.76 1.99 18.40 12.94
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
10.11.2020 19:19:04
FZ9242-1.JDF
7.27
7.35
7.46
7.39
7.47
7.61
7.28
7.62
6.38
7.34
7.37
7.40
6.36
6.67
7.29
6.69
6.37
6.39
6.35
15.49 19.09 36.02 26.24 10.05 9.46
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3
10.11.2020 19:19:34
FZ9242-1.JDF
4.53
4.54
4.70
4.69
4.63
4.64
5.84
5.84
5.70
5.71
5.70
4.80
4.79
7.94 0.88 3.76 1.99 19.18 8.21 18.41
5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5
10.11.2020 19:27:44
2.07
2.03
FZ9242-1.JDF
2.02
3.36
2.51
3.33
2.01
2.00
2.02
27.09 12.94
3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0
For Table 6 Line 5
10.11.2020 18:40:06
3.35
FZ9240-1.JDF
2.07
2.03
2.50
7.26
3.33
2.51
2.50
4.53
7.35
4.54
4.69
7.39
4.68
7.46
7.61
7.62
2.02
0.00
6.38
6.36
6.67
5.84
6.69
6.37
5.85
6.39
6.35
4.64
2.34
5.82
5.27
2.00
5.25
5.70
4.80
2.29
6.73
18.85 30.52 10.05 9.78 1.13 1.25 1.17 16.27 12.86 3.39
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
10.11.2020 18:40:49
FZ9240-1.JDF
7.26
7.35
7.39
7.46
7.61
7.47
7.27
7.62
7.33
7.37
7.40
6.38
7.29
6.36
6.67
6.69
6.37
6.39
6.35
6.73
18.85 22.50 41.47 30.52 10.05 9.78
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3
10.11.2020 18:41:13
FZ9240-1.JDF
4.53
4.54
4.69
4.68
5.84
5.85
4.64
4.63
5.82
5.27
5.25
5.70
4.80
4.79
4.79
4.80
7.88 1.13 1.25 1.17 19.82 2.21 16.27
5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5
10.11.2020 18:41:34
3.35
FZ9240-1.JDF
2.07
2.03
2.50
3.33
2.51
2.50
2.02
2.34
2.00
2.29
12.86 28.28 3.39
3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0
For Table 6 Line 6
10.11.2020 19:05:09
2.07
FZ9241-1.JDF
2.03
3.35
2.50
7.26
2.02
4.54
4.53
3.33
7.35
7.46
4.70
4.68
7.47
7.61
7.62
0.00
6.67
6.38
5.84
6.36
6.69
4.63
6.39
6.35
5.70
2.00
2.34
4.80
5.71
15.05 26.02 10.03 9.44 1.90 1.62 18.30 34.83
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
10.11.2020 19:05:57
FZ9241-1.JDF
7.26
7.35
7.46
7.39
7.47
7.27
7.61
7.62
7.33
7.36
7.40
7.29
6.67
6.38
6.36
6.69
6.37
6.39
6.35
15.05 19.50 36.01 26.02 10.03 9.44
7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3
10.11.2020 19:06:22
FZ9241-1.JDF
4.54
4.53
4.70
4.68
5.84
4.63
4.64
5.70
4.80
4.79
4.80
4.79
5.71
8.20 0.71 1.90 1.62 19.03 3.74 18.30
5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5
10.11.2020 19:13:05
2.07
FZ9241-1.JDF
2.03
3.35
2.50
2.02
3.33
2.00
2.34
34.84
3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0

Om0c00647 Si 001

Uploaded by

Copyright:

Available Formats

Om0c00647 Si 001

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Om0c00647 Si 001

Uploaded by

Copyright:

Available Formats

Supporting information

Influence of the N→Ru coordinate bond length on the

General information …………………………………………………………………………………………………………………………………………… S2

Synthesis of the complex (3) (dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-

Preparation of [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene] (dichloro)[2-(3,4-

Procedure for the self-cross-metathesis reaction.

Procedure for the cross-metathesis reaction.

Experimental part for X-ray analysis

Ru(1)─C(38) 1.8316(17) 1.826(2) 1.8294(11) 1.8325(11) 1.820(3) – 1.831(3) 1.815(4)

Ru(1)─C(2) 2.0431(17) 2.0352(18) 2.0370(10) 2.0303(10) 2.015(3) – 2.027(3) 2.027(5)

Ru(1)─N(2) 2.2233(15) 2.2428(15) 2.2274(9) 2.2969(9) 2.323(2) – 2.340(2) 2.251(4)

Ru(1)─Cl(1) 2.3511(4) 2.3668(5) 2.3516(3) 2.3632(3) 2.3582(7) –2.3668(7) 2.3517(13)

Ru(1)─Cl(2) 2.3602(4) 2.3562(5) 2.3545(3) 2.3594(3) 2.3704(7) –2.3820(7) 2.3537(12)

N(2)─C(41) 1.505(2) 1.492(3) 1.5045(14) 1.5045(14) 1.483(3) – 1.494(3) 1.492(5)

N(2)─C(45) 1.523(2) 1.494(2) 1.5092(14) 1.5092(14) 1.483(3) – 1.496(3) 1.493(5)

N(2)─C(37) 1.488(2) 1.486(2) 1.4931(14) 1.4931(14) 1.478(4) – 1.488(4) 1.496(5)

C(32)─C(37) 1.500(2) 1.495(3) 1.4991(17) 1.4991(17) 1.499(4) – 1.501(4) 1.491(6)

C(31)─C(32) 1.416(2) 1.418(3) 1.4129(16) 1.4129(16) 1.398(4) – 1.405(4) 1.404(6)

C(31)─C(38) 1.467(2) 1.457(3) 1.4610(15) 1.4610(15) 1.460(3) – 1.471(3) 1.468(6)

N(1)─C(2) 1.351(2) 1.346(3) 1.3493(13) 1.3493(13) 1.331(3) – 1.341(3) 1.347(5)

N(1)─C(5) 1.478(2) 1.479(2) 1.4768(15) 1.4768(15) 1.479(3) – 1.485(3) 1.473(6)

N(3)─C(2) 1.357(2) 1.351(3) 1.3569(14) 1.3569(14) 1.351(3) – 1.353(3) 1.360(5)

N(3)─C(4) 1.474(2) 1.478(2) 1.4733(14) 1.4733(14) 1.473(3) – 1.477(3) 1.472(6)

C(4)─C(5) 1.518(3) 1.510(3) 1.5157(18) 1.5157(18) 1.511(4) – 1.529(4) 1.515(6)

C(38)─Ru(1)─C(2) 99.60(7) 100.90(8) 98.72(4) 98.72(4) 98.64(12) – 99.06(12) 99.31(19)

C(38)─Ru(1)─N(2) 88.35(6) 89.72(7) 88.22(4) 88.22(4) 92.01(10) – 93.14(10) 87.69(17)

C(2)─Ru(1)─N(2) 170.93(6) 168.80(7) 172.67(4) 172.67(4) 167.79(10) – 169.00(10) 172.84(16)

C(38)─Ru(1)─C1(1) 100.00(5) 97.21(6) 101.55(4) 101.55(4) 95.35(8) – 97.20(9) 98.58(15)

C(2)─Ru(1)─C1(1) 84.74(5) 85.44(5) 88.81(3) 88.81(3) 91.10(7) – 92.22(7) 88.11(13)

N(2)─Ru(1)─C1(1) 89.61(4) 89.72(4) 87.48(2) 87.48(2) 87.14(5) – 87.92(6) 89.38(10)

C(38)─Ru(1)─C1(2) 101.99(5) 99.38(6) 99.98(4) 99.98(4) 92.51(9) – 92.76(8) 100.49(15)

C(2)─Ru(1)─C1(2) 95.43(5) 92.58(5) 90.15(3) 90.15(3) 86.22(7) – 87.52(7) 89.45(13)

N(2)─Ru(1)─C1(2) 87.11(4) 89.16(4) 90.97(2) 90.97(2) 91.50(6) – 92.54(6) 90.75(10)

C1(1)─Ru(1)─C1(2) 157.658(17) 163.364(19) 158.354(11) 158.354(11) 170.25(3) – 172.03(3) 160.92(4)

C(37)─N(2)─Ru(1) 109.21(10) 108.02(11) 111.04(6) 111.04(6) 106.86(17) – 107.64(17) 108.8(3)

C(31)─C(38)─Ru(1) 128.74(13) 128.94(14) 130.39(8) 130.39(8) 122.9(2) – 123.7(2) 129.5(3)

N(1)─C(2)─Ru(1) 132.21(12) 132.92(15) 131.95(8) 131.95(8) 134.5(2) – 135.6(2) 131.3(3)

N(3)─C(2)─Ru(1) 120.24(12) 119.33(14) 121.09(7) 121.09(7) 117.1(2) – 117.4(2) 122.2(3)

Figure S1. Solid-state crystal structure of compound 5a

Table S3. Bond lengths for 5a.

Table S4. Bond angles for 5a.

C(38) Ru(1) N(2) 88.35(6) C(13) C(14) C(18) 120.3(2)

Table S5. Hydrogen bonds for 5a.

Figure S2. Solid-state crystal structure of compound 5b

Table S6. Bond lengths for 5b.

Table S7. Bond angles for 5b.

C(38) Ru(1) Cl(2) 99.38(6) C(15) C(16) C(19) 118.6(2)

Table S8. Hydrogen bonds for 5b.

Figure S3. Solid-state crystal structure of compound 5c

Table S9. Bond lengths for 5c.

Table S10. Bond angles for 5c.

Table S11. Hydrogen bonds for 5c.

Figure S4. Solid-state crystal structure of compound 5d

Table S12. Bond lengths for 5d.

Table S13. Bond angles for 5d.

Table S14. Hydrogen bonds for 5d.

Figure S5. Solid-state crystal structure of compound 5e

Table S15. Bond lengths for 5e.