A New Type of Coordination in Copper(I) Complexes with Trivalent Phosphorus Compounds Containing Phosphorus-Sulfur Bonds

Transformation of copper(I) thiophosphite complexes into copper(I) clusters bridged by diisopropyldisulfides and diethyldisulfides

“…We have revealed that some complexes of Cu(I) halides with thioesters of the P(III) acids may be transformed into copper(I) clusters with Cu· · ·Cu short contacts, e.g., [(i-PrS) 3 P·Cu 4 Cl 4 ] n . Copper clusters are bound via bridge trithiophosphite molecules, the unusual tridentate Cu coordination by P and two S atoms being realized in crystals [8].…”

“…In the present work, we describe chemical transformations observed in polymeric and tetrameric Cu(I) complexes with thiophosphite ligands upon recrystallization and storage. It was shown that tetrameric cuban-like derivatives with monodentate coordination of copper atoms, [(RS) 3 P·CuX] 4 , 1 and 2, as well as the polymeric bidentate complexes [(RS) 3 P·CuX] n , 3, whose structures were determined earlier [6,8], are transformed into polymeric clusters [(RS) 2 ·2CuX] n 4-6 at the storage or upon recrystallization in polar solvents (CHCl 3 and CH 3 CN):…”

“…Coordination properties of thiophosphites were found to be essentially different from their oxygen and nitrogen analogues [1][2][3][4][5][6]. It has been shown earlier that the diversity of coordination modes of copper(I) complexes with P(III) thioesters was determined by the electronic structure and lability of thiophosphite ligands.…”

“…This flexibility and the presence of several donor atoms in these ligands determine the copper coordination chemistry, which appeared to be diverse and unexpected. The dimeric, tetrameric step-like and cuban-like, as well as the polymeric chain and two-dimensional polymeric structures have been realized in studied complexes [3][4][5][6][7][8].…”

“…causing the disproportionation of ligands and their full or partial substitution in metal coordination sphere as well as other transformations. These result in structural changes: from polymeric or cuban-like complexes to dimeric structures as well as in the chemical transformations of ligands [3,4,7,8].…”