Reactions of sulfido-tricobalt cluster (μ3-S)Co3(CO)7(μ-C,N-C5H4N) with diphosphine ligands and (μ3-S)Co3(CO)7(μ-S,P-SPMe2) towards diphenyl-2-pyridylphosphine

Reaction of sulfido-tricobalt cluster, (μ3-S)Co3(CO)7(μ-S,P-SPMe2) (8), with PPh2py in THF at 90 °C for 6 h gave two compounds, (μ3-S)Co3(CO)5(μ-S,P-SPMe2)(μ-P,N-PPh2py) (9) and (μ3-S)Co3(CO)4(μ-S,P-SPMe2)(μ-P,N-PPh2py)(PPh2py) (10). Both compounds, 9 and 10, were well characterized by spectroscopic means as well as X-ray crystal structure determination. The hybrid bidentate PPh2py ligand bridges two cobalt centers in 9 (or 10) through both phosphorus and nitrogen atoms. Besides the bridging PPh2py ligand, one more additional coordinating PPh2py ligand attached through phosphorous was observed at 10. Treatment of another sulfido-tricobalt cluster (μ3-S)Co3(CO)7(μ-C,N-C5H4N) (2a) with bis(diphenylphosphino)methane (DPPM) in THF at 25 °C for 2 h gave two DPPM bridged complexes (μ3-S)Co3(CO)5(μ-C,N-C5H4N)(μ-P,P′-DPPM)] (11) and (μ3-S)Co3(CO)5[(μ-C(O),N-C5H4N(CO))(μ-P,P′-DPPM)] (12) where as bis(diphenylphosphino)ethane (DPPE) gave two DPPE bridged isomeric complexes (μ3-S)Co3(CO)5[(μ-C(O),N-C5H4N(CO))(μ-P,P′-DPPE)] (13a and 13b). The X-ray structural analyses of 12 and 13b revealed that carbonylation occurred at the CoC(pyridyl) bond.