Disulfide Versus Diselenide Complexes of Copper: Air-Free and Air-Exposed Syntheses Result in Variable Ligands and Coordination

Authors

Jamie M. Murphy Ph.D., Harding UniversityFollow
Amanda M. Owen, Clemson UniversityFollow
Colin D. Millen, Clemson UniversityFollow
Julia L. Brumaghim Ph.D., Clemson UniversityFollow

Document Type

Article

Publication Title

Journal of Chemical Crystallography

Publication Date

8-25-2023

Volume

53

Issue

December 2023

First Page

515

Last Page

528

Abstract

Reactions of bis(1-methylimidazole-2)disulfide (MMI^DS) or bis(1-methylimidazole-2)diselenide (MMI^DSe) with Cu(I) result in a variety of products depending on conditions. Under air-free conditions, dinuclear complexes [Cu2(µ,κ^S-MMI)2(κ^N,N’-MMI^DS)2][BF4]2 and [Cu2(µ,κ^Se-MMI^Se)2(κ^N,N’-MMI^DSe)2][BF4]2 were obtained and structurally characterized. Both complexes show reduction of the MMI^DS or MMI^DSe and subsequent bridging of the thione or selone between the dinuclear Cu(I) centers. Combining MMI^DSe with Cu(I) in air resulted in crystallization of three different complexes from the same reaction mixture, as confirmed by X-ray crystallography. The various products, [Cu(κ^N,N’-MMI^MSe)(κ^N,N’-MMI^TSe)(CH3CN)][BF4]2, [Cu(κ^N,N’-MMI^Se-CH2-MMI^Se)2[BF4]2, and the co-crystallized [[Cu(κ^N,N’-MMI^DSe)2][Cu(κ^N,N’-MMI^Se-CH2-MMI^Se)][BF4]4, indicate that significant reactivity occurs with the availability of air and CH2Cl2 solvent. In addition to oxidation of Cu(I) to Cu(II), the MMI^DSe ligands also react to form monoselenide, triselenide, and Se-CH2-Se bridged selenide ligands.

Copyright held by

Springer Nature

Recommended Citation

Murphy, J. M., Owen, A. M., Millen, C. D., & Brumaghim, J. L. (2023). Disulfide Versus Diselenide Complexes of Copper: Air-Free and Air-Exposed Syntheses Result in Variable Ligands and Coordination. Journal of Chemical Crystallography, 53 (December 2023), 515-528. http://dx.doi.org/https://doi.org/10.1007/s10870-023-00991-3