Reaction of thioesters and thiolactones with cyclopentadienylmetal dicarbonyl dimers

Article abstract of DOI:10.1021/om50004a004

Complexes containing a metal-metal triple bond, (RC₅H₄)₂M₂(CO)₄ (R = H, CH₃; M = Mo, W), react with thioesters and thiolactones to give compounds of type (thioester or thiolactone) M₂(CO)₄(C₅H₄R). Analytical and spectral data, together with an X-ray analysis of the (thiobutyrolactone)molybdenum complex, revealed that the sulfur is bonded to both molybdenum atoms and that a semibridging carbonyl group is present. There is no evidence for bonding of the oxygen, of the organic ligand, to a metal atom. Crystal data for [(C₅H₅)₂Mo₂(CO)₄(SC ₄H₆O)]: tetragonal space group P4₂bc, a = 19.872 (3) ?, c = 9.643 (2) ?, V = 3808.0 ?³, Z = 8. The intensities of 1384 reflections with I > 2.3σ(I), collected by counter methods with Mo Kα radiation, were used in the least-squares refinement. Final R_F = 0.021 and R_wF = 0.025. The bridgehead C atom is bonded to one Mo atom while S bridges between both Mo atoms: Mo(1)-Mo(2) = 3.138 (1) ?, Mo(2)-C = 2.235 (6) ?, Mo(1)-S = 2.402 (1) ?, Mo(2)-S = 2.385 (2) ?, and S-C = 1.807 (6) ?. There is a semibridging carbonyl group: Mo(2)-C(21) = 1.944 (6) ?, Mo(1)?C(21) = 2.764 (8) ?, and Mo(2)-C(21)-0(21) = 162.7 (7)°.