Sulfur dioxide insertion. VI. S-sulfinatopentacarbonyl complexes of group VI and VII transition metals

Article abstract of DOI:10.1021/ic50066a007

A number of sulfinatopentacarbonyls of manganese(I) and rhenium(I) have been prepared by the reactions of M(CO)₅R (M = Mn, R = CH₃, C₂H₅, and CH₂C₆H₅; M = Re, R = CH₃ and CH₂C₆H₅) with refluxing sulfur dioxide and of Mn-(CO)₅C₆H₅ with liquid SO₂ at 35-45° under pressure. Complexes containing the anions Cr(CO)₅(SO₂C₆H₅)^- and W(CO)₅-(SO₂C₆H₅)^-, the former being isoelectronic with Mn(CO)₅(SO₂C₆H₅), were obtained from M(CO)₅I^- (M = Cr and W) and sodium benzenesulfinate, but the analogous Mo(CO)₅(SO₂C₆H₅)^- could not be prepared. Other attempted syntheses of M(CO)₅(SO₂R) (M = Mn and Re) are described and briefly discussed. All of the sulfinatopentacarbonyl complexes prepared have been assigned structures containing M-S(O)₂-R linkages from the infrared and proton magnetic resonance spectral data. The infrared carbonyl stretching region spectra of the manganese and rhenium S-sulfinatopentacarbonyls are tabulated and the magnitude of the splitting of the E band is discussed in terms of the size of the metal and bulkiness of substituents on the α-carbon atom of R. Thermal and photolytic treatment of Mn(CO)₅(SO₂CH₂C₆H₅) provided no evidence of desulfurylation to give Mn(CO)₅CH₂C₆H₅.