Reactions of dinuclear and polynuclear complexes. Part 18 substitution reactions of a μ-chloro or a μ-thiolato ligand in the dinuclear cyclopentadienyl molybdenum(III) complex [Cp2Mo2( μ-Cl)( μ-SMe)3]

Article abstract of DOI:10.1016/S0022-328X(97)00082-X

Thermal reaction of the chloro-bridged complex [Cp₂Mo₂( μ-Cl)( μ-SMe)₃] 1 with the dithiols HS(CH₂)_nSH (n = 2 or 3) affords the quadruply thio-bridged complexes [Cp₂Mo₂{ μ-S(CH₂)_nSH}( μ-SMe)₃] where n = 2 (2) or 3 (3). 2 has been shown by X-ray diffraction to contain the μ-η¹-dithiolate ligand ^-S(CH₂)₂SH which bridges an Mo-Mo single bond whose length is 2.606(1) A. The substitution reaction of the chloro bridge in 1 also occurs with phenylphosphine, H₂PPh, giving the μ-phosphido compound [Cp₂Mo₂( μ-HPPh)( μ-SMe)₃] 4. In contrast with diphenylphosphine, HPPh₂, the thiolate ligand trans to the chloro bridge is replaced by a PPh₂ group, giving the new μ-chloro complex [Cp₂Mo₂( μ-Cl)( μ-PPh₂)( μ-SMe)₂ 5. All new products have been characterized by spectroscopic analyses.