Synthesis and Structural Characterization of Cobalt, Nickel and Copper Phosphanylthiolato Complexes

Neutral cobalt, nickel and copper complexes of a series of phosphanylthiol ligands PhnP(C6H4SH‐2)3–n (n = 1, 2) have been synthesized and characterized by IR and NMR (1H and 31P) spectroscopy, FAB mass spectrometry and X‐ray structural analysis. All of the compounds, with the exception of [Co{Ph2PC6H4S‐2}2], were synthesized by electrochemical oxidation of the anodic metal (cobalt, nickel or copper) in an acetonitrile solution of the appropriate ligand and a small amount of tetramethylammonium perchlorate as an electrolytic carrier. The presence of an additional coligand (PPh3, dppe, dppm or bipy) in the cell led to the synthesis of mixed complexes in one step. The crystal structures of [Co{Ph2P(O)C6H4S‐2}2] (1), [Co2{PhP(C6H4S‐2)2}2(μ‐N2)(bipy)2] (2), [Ni2{PhP(C6H4S‐2)2}2] (3), [Ni2{PhP(C6H4S‐2)2}2(μ‐dppe)]·CH2Cl2 (4), [Cu2{Ph2PC6H4S‐2}2(PPh3)2] (5), [Cu2{PhP(C6H4S‐2)2}(PPh3)2(CH3CN)] (6), [Cu2{Ph2PC6H4S‐2}2(μ‐dppe)] (7) and [Cu2{Ph2PC6H4S‐2}2(μ‐dppm)] (8) are discussed. Neutral cobalt, nickel and copper complexes of a series of phosphanylthiol ligands PhnP(C6H4SH‐2)3–n (n = 1, 2) have been synthesized by electrochemical oxidation of the anodic metal. The presence of an additional coligand in the cell led to the synthesis of mixed complexes in one step. The crystal structures and spectroscopic properties of these compounds are reported.