Characterization of the Products from the Reaction of Copper(II) Bromide and Tetramethylthiuram Sulfide: An Undergraduate Project Involving Two Unknown Metal Complexes and an Unexpected Pattern of Reactivity

Abstract

A senior undergraduate project in inorganic chemistry is described, involving the reaction of copper(II) bromide and the potential bidentate sulfur ligand bis(N,N-dimethylthiocarbamoyl) sulfide (N,N,N',N'-tetramethylthiuram monosulfide). The students are required to interpret the unusual pattern of reactivity observed, and to characterize the products generated, bromo-bis(N,N-dimethylthiocarbamoyl)sulfidocopper(I) and 2,5-bis(N,N-dimethyliminium)-1,3,4-trithiolane tribromocuprate(I), by means of elementary analyses, infrared spectroscopy, and magnetic susceptibility measurements. Additional topics for discussion are suggested. The behavior of the reactants in this system would not normally be evident to students at an undergraduate level, but would be accessible after rigorous interpretation of the experimental evidence.

Copper(III) Dithiocarbamates. An Undergraduate Experimental Project with Unexpected Challenges

“…In the product, the first absorption is found at 1604, and the absence of bands between 800 and 1000 cm ᎑1 is more reminiscent of the spectrum of a chelated dialkyldithiocarbamate than of the parent disulfide. Thus the nature of the product is a consequence of the reductive cleavage of the original disulfide to dithiocarbamate and is not due to oxidative cyclic cation formation, as was the case for the monosulfide (1). A vast amount of literature is available in support of the oxidative properties of thiuram disulfides (2).…”

“…A short account of one such system has been published (1). In our students' view, coordination compounds are "predictable" or "unchallenging" when compared to the bewildering array of possibilities offered by the other branches of chemistry.…”

“…We endeavor to use examples from our own current research to present the students with examples of experiments that are not quite predictable. A short account of one such system has been published (1).…”

Synergistic Effect of Copper Sulfate and Tetramethylthiuram Monosulfide Induced Metal‐Coordination Cross‐Linking in Nitrile–Butadiene Rubber

“…Introducing the TMTM into the coordinated cross-linking system of NBR/CuSO 4 blends, the synergistic coordination effect between radicals and copper ions might be formed, which is expected to endow a great improvement of the properties of vulcanizates. Contreras, Victoriano, and Wu et al [34][35][36] investigated the chemical reaction between Cu 2+ and TMTM and explored the usefulness and attractiveness of the reaction products in different fields.…”

Development of a Research-Oriented Inorganic Chemistry Laboratory Course

“…The value of research as a component of undergraduate education is widely recognized, and recent efforts to introduce undergraduate students to research experience have taken various forms in the United States and other countries (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11). During the past 20 years, the chemistry department of Virginia Commonwealth University has consistently involved undergraduate students in research through the elective research and NSF-sponsored Experience for Undergraduates (REU) programs.…”