Molecular structure and spectroscopic properties of [Co(Me2dtc)2{(Ph2PO)2BF2}] (Me2dtc = N,N-dimethyldithiocarbamate)

Oxidation of a blue ethanolic mixture containing Co(BF4)2·6H2O and PClPh2 by tetramethylthiuram disulfide afforded a red-colored complex having a cis-[CoIII(Me2dtc)2(P)2] environment (Me2dtc− = N,N-dimethyldithiocarbamate), although the yield was relatively low. Single-crystal X-ray crystallography revealed that the product was [Co(Me2dtc)2{(Ph2PO)2BF2}] (1), where bis(diphenylphosphinito)difluoroborate was probably formed by hydrolysis of PClPh2 followed by reaction with BF4− in ethanol. The same complex was also prepared by hydrolysis of cis-[Co(Me2dtc)2(PHPh2)2]BF4 in a mixture of acetonitrile, methanol and water. The molecular structure and spectroscopic properties of complex 1 were compared with those of the corresponding Ph2POMe complex, cis-[Co(Me2dtc)2(Ph2POMe)2]BF4.