Old Copper Complex

The Old Copper Complex of the Upper Midwest United States lasted from about 3000 to 1000 B.C. spanning the late Middle Archaic and the early Late Archaic (Gibbon 1998:27). During that time the indigenous peoples manufactured copper tools, ornaments and weapons without the aid of smelting or casting. The period is also noted for a lack of ceramic manufacture, or any other pyrotechnology.
Artifacts from the Archaic and Old Copper Complex have been known since the turn of the last century, but little has been written about how copper tools were manufactured during this period. While smelting and casting were not used, it has been seen that techniques using temperatures high enough to anneal copper have been employed. The type of socketed spearhead classified by Wittry as 1A has a triangular cross section and a socket formed with flanges bent in an even 90 degree angle for their length (Wittry 1957: 210). Creating this type of spearhead with only hammerstones and anvils would be difficult and inefficient.

The Old Copper Complex and its hefty, utilitarian, copper artifacts have been a focus of North American archaeological research for almost a century. The Milwaukee Public Museum (MPM) holds the largest collection of Old Copper Complex material culture, including a copper crescent with unique provenience. Previous research has indicated that Archaic exportation of Old Copper Complex copper tools extended as far south as St. Louis, however the MPM crescent was unearthed near Chattanooga, Tennessee. While Archaic trade routes crisscrossed North America, the presence of Old Copper Complex material culture is extremely rare to the archaeological record of Tennessee. Burials at Old Copper Complex and Late Archaic Tennessee sites have included copper from the Lake Superior area and marine shell from the Gulf Coast, which indicates that these social groups were involved in similar trade routes and may have had direct or down-the-line political and trade relationships.

The presence of this rare trade good in the Late Archaic archaeological record of Tennessee is indicative of a changing social environment. Once becoming involved with extensive trade routes and the exotic goods they bring, this Tennessean egalitarian society began to take on a transegalitarian structure. During this transitional period between an egalitarian and ranked social models, aggrandizers would have used exotic goods such as the copper crescent to gain influence within the community.  The existence of the Old Copper Complex crescent and other exotic trade goods in Archaic Tennessee sites point to the increasing importance on wealth goods in this changing social environment.

In 2004, the U.S. Army Corps of Engineers (USACE), St. Paul District, contracted
Florin Cultural Resource Services (FCRS) to conduct a Phase III data recovery at a portion of
the Sandy Lake Dam site (21AK11) prior the expansion of an existing comfort station in the
Sandy Lake Recreation Area. The Sandy Lake Dam site is a multi-component site with
occupations from the Old Copper complex phase of the Archaic period, of which little is
known in the state of Minnesota, as well as the Late Woodland and Historic periods. The site
has integrity, containing intact stratified cultural deposits with an Old Copper component
below a Late Woodland component. This thesis research focuses on the Old Copper complex
component of the portion of the Sandy Lake Dam site that was excavated during the 2004
FCRS data recovery. Copper artifacts were analyzed and typed, and lithic tools associated
with the intact Old Copper component of the site were re-examined. The Old Copper
component was compared and contrasted to other Old Copper complex sites in Minnesota.
The site also presented an opportunity to add information to the database of Fat Rock Quartz,
which has only recently been recognized as a distinctive lithic raw material type. A new
radiocarbon date from the Old Copper component of the site is discussed. Conclusions based
on the artifact assemblage, patterning, and the radiocarbon date are discussed in regards to site
function. The radiocarbon date from the Sandy Lake Dam site provides solid evidence that
Archaic inhabitants of northeastern Minnesota were actively involved in the early part of the
Old Copper complex, well over six thousand years ago.

Avocational collectors in Wisconsin have collected thousands of copper artifacts over the last century and half.  This copper has gone largely unexamined by the professional archaeological community.  The archaeological literature is therefore silent on basic facts such as size ranges and changes in use of the raw material from society to society.  Copper entered the economic systems of these Archaic Wisconsin societies as an innovative, but ultimately redundant raw material given the existence of bone and stone artifacts of apparently equivalent use-value.  It is expected that copper as a raw material fundamentally changed the cultural systems of its adoptive societies and that its use will vary relative to its accessibility.  This study reports in-progress results from a large copper collection from both Lake Koshkonong in southeast Wisconsin and Lake Nokomis in Northern Wisconsin.  The use of copper as a raw material will be illustrated from the southern Wisconsin locale using metric, morphological, and use wear data.

This report considers copper crescent-shaped objects from Ontario, contextualizing them within broader archaeological discussions of the Old Copper Complex. I focus on a small assemblage of antiquarian-collected crescents from the Royal Ontario Museum. A literature review comprises the bulk of this report; crescents recovered from sites located in the center of the Old Copper Complex, in current-day Wisconsin and Michigan, help to situate examples in the antiquarian collection. I discuss crescents in terms of their chronolo- gical and geographic breadth, their formal variation, and the different depositional contexts in which they are found. Three examples from the antiquarian collection represent novel forms of copper crescent that are not represented in the accepted typology. Two of these, collected approxima- tely 1,600 km apart from one another, closely resemble stone and copper ulu knives, each with a unique copper handle that once bore a haft. By situating this particular collection within broader discussions of native copper, this report demonstrates the continued importance of thinking through poorly- contextualized archaeological collections while remembering the limitations of rigid, typological thinking.

A study of Cu–O vibration frequencies in 32 isostructural mixed copper complexes containing eight differently substituted phenanthrolines and four different oxygen donor bidentate ligands, is presented. In all cases linear correlation was found between phenanthroline pKa values and the studied vibration frequencies, suggesting that an increase in phenanthroline basicity weakens Cu–O bonds in this type of compound.

The system formed by Cu (II) and 2, 2′-bipyridine (bpy) has been revisited by use of EPR and electronic absorption spectroscopies. The mono-chelated [Cu (bpy)] 2+, bis-chelated trans-[Cu (bpy) 2] 2+ with pseudo-tetrahedral geometry due to the steric hindrance of the 3 ...

Trifluoromethoxy functionalized copper(II) Schiff base complexes N,N′-bis(5-trifluoromethoxysalicylaldehyde)cyclohexanediiminatodiaquacopper(II) and N,N′-bis(5-trifluoromethoxysalicylaldehyde)phenylenediiminatocopper(II) were synthesized and characterized. Thermal decompositions of the synthesized complexes were studied by thermogravimetry in order to evaluate their thermal stability and thermal decomposition pathways. Three similar decomposition steps occurred for the two copper complexes. Mass losses and evolved gasses were characterized by TG/DTA-MS. Kinetic parameters were calculated and the results showed that the values obtained are comparable.

Three thiophene-2,5-dicarboxylic acid (H2tdc) complexes of copper(II) with 2-aminomethylpyridine (ampy), {[Cu2(μ-tdc)2(ampy)2]·2DMF}n (1), ethylenediamine (en), trans-[Cu(H2O)2(en)2](tdc) (2) and 4-methylimidazole (4-meim), trans-[Cu(H2O)2(4-meim)4](tdc)·4H2O (3) have been synthesized and characterized by spectral (IR, UV–Vis), thermal analyses and X-ray diffraction techniques. In 1, thiophene-2,5-dicarboxylate acts as a bridging bis(bidentate) ligand through four carboxylate oxygen atoms forming a 1-D zigzag polymeric chain, whereas in 2 and

A series of complexes of MIIX2 transition metal salts (X = ClO4, M = Co, Ni, Cu, Zn; X = Cl, M = Cu, Zn) with a calix[4]arene substituted at the lower rim {L = 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis[(dimethylphosphinoyl)methoxy]calix[4]arene} are isolated and characterized. Two different stoichiometries are evidenced, 1:1 for the CoII, NiII, and CuII complexes, independently of the anion (Cl− or ClO4−), as well as for the Zn(ClO4)2 complex, while a 2:1 metal/ligand ratio is found for the complex with ZnCl2. The coordination mode and structure of the complexes are investigated by several spectroscopic and magnetochemical methods, both in the solid state and in solution. Coordination through the phosphoryl groups of the ligand is ascertained by X-ray diffraction and IR and NMR spectroscopic data. The crystal structure of the 2:1 Zn compound (triclinic, P , Z = 2) shows the presence of the tetrametallic species Zn4L2 with three different tetrahedral Zn environments, ZnCl2O2, ZnCl3O, and ZnClO3, the latter bridging two ligand molecules. Magnetic susceptibility, EPR data, and electronic spectra are indicative of a tetrahedral arrangement of the ligands in the CoII (high-spin d7) 1:1 complex, which is also most probably the ligand geometry in the NiII and CuII 1:1 complexes. In solution, the extent of the interaction between L and the MII ions has been determined by UV/Vis spectrophotometric titrations. The resulting stability constants for 1:1 complexes are in the range log K1 = 4.8−5.4. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)