Mononuclear copper(I) complexes of O-t-butyl-1,1-dithiooxalate and of O-t-butyl-1-perthio-1-thiooxalate

Described are the syntheses and structures of a phosphonium salt of the anionic ligand O-t-butyl-1,1-dithiooxalate, [PPh3Bz][i-dtotBu] ([PPh3Bz][1]), and of two Cu(I) complexes of this anion, Cu(PPh3)2(η2-i-dtotBu) (2) and Cu(dmp)(PPh3)(η1-i-dtotBu) (3, dmp = 2,9-dimethyl-1,10-phenanthroline). In addition, it was found that the reaction of CuBr2 with i-dtotBu− gives a O-t-butyl-1-perthio-1-thiooxalato complex of copper(I), [BzPh3P][Cu(Br)(S-i-dtotBu)] ([BzPh3P][4]), where [S-i-dtotBu]− is a disulfide-containing anionic ligand. The electronic structure and absorption spectrum of this species were investigated by time dependent DFT methods.