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

Neutral cobalt, nickel and copper complexes of a series of phosphanylthiol ligands Ph n P(C 6 H 4 SH‐2) 3– n ( n = 1, 2) have been synthesized and characterized by IR and NMR ( 1 H and 31 P) spectroscopy, FAB mass spectrometry and X‐ray structural analysis. All of the compounds, with the exception of [Co{Ph 2 PC 6 H 4 S‐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 (PPh 3 , dppe, dppm or bipy) in the cell led to the synthesis of mixed complexes in one step. The crystal structures of [Co{Ph 2 P(O)C 6 H 4 S‐2} 2 ] ( 1 ), [Co 2 {PhP(C 6 H 4 S‐2) 2 } 2 (μ‐N 2 )(bipy) 2 ] ( 2 ), [Ni 2 {PhP(C 6 H 4 S‐2) 2 } 2 ] ( 3 ), [Ni 2 {PhP(C 6 H 4 S‐2) 2 } 2 (μ‐dppe)] · CH 2 Cl 2 ( 4 ), [Cu 2 {Ph 2 PC 6 H 4 S‐2} 2 (PPh 3 ) 2 ] ( 5 ), [Cu 2 {PhP(C 6 H 4 S‐2) 2 }(PPh 3 ) 2 (CH 3 CN)] ( 6 ), [Cu 2 {Ph 2 PC 6 H 4 S‐2} 2 (μ‐dppe)] ( 7 ) and [Cu 2 {Ph 2 PC 6 H 4 S‐2} 2 (μ‐dppm)] ( 8 ) are discussed.