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]
Résumé
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) Å. 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. © 1997 Elsevier Science S.A.