Copper(I) oxalate complexes: Synthesis, structures and surprises

Autor: Gilles André, Dylan C. Kelly, Robert J. Papoular, A. Timothy Royappa, Banghao Chen, Nikolaos Kourkoumelis, Allegra M. Pekarek, Deke M. Blum, Andrew D. Mercer, Matthew R. Suchomel, Andrew D. Royappa, Oliver D. Vu, Jacob R. Stepherson, Arnold L. Rheingold, Raphael F. Moral, James A. Golen, Tien Q. Duong
Rok vydání: 2016
Předmět:
Zdroj: Polyhedron. 119:563-574
ISSN: 0277-5387
DOI: 10.1016/j.poly.2016.09.043
Popis: A series of dinuclear copper(I) oxalate complexes was synthesized by the direct acid-base reaction of Cu2O with oxalic acid in ethanol with a ligand, or in neat ligand. The complexes incorporated a variety of ligands L (L = triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, triphenylphosphite, diisopropyl sulfide, cyclooctadiene and cyclohexylisocyanide) and had the general formula LnCu(μ2-C2O4)CuLn (n = 1 or 2). The CuI/CuII mixed-valence trinuclear compound (iPr2S)2CuI(C2O4)CuII(C2O4)CuI(iPr2S)2 was formed concomitantly with the target dinuclear Cu2C2O4(iPr2S)4 complex, shedding light on the mechanism of disproportionation of this family of complexes. With norbornadiene (nbd) as a ligand, however, a coordination polymer Cu2C2O4(nbd) was formed. Also, the same reaction with L = 2,9-dimethyl-1,10-phenanthroline or pyridine resulted in the known tetrahedral complex ions [CuLm]+ (m = 2 or 4). Lastly, the ligand di-2-(1-di-(2-picolyl)amino)propyl disulfide produced not the expected Cu(I) oxalate complex, but a Cu(II) picolylamine oxalate coordination polymer. All products were structurally characterized by single-crystal X-ray diffraction if soluble, and by powder X-ray diffraction methods if not.
Databáze: OpenAIRE
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