REACTIONS OF DINUCLEAR AND POLYNUCLEAR COMPLEXES .18. SUBSTITUTION-REACTIONS OF A MU-CHLORO OR A MU-THIOLATO LIGAND IN THE DINUCLEAR CYCLOPENTADIENYL MOLYBDENUM(III) COMPLEX [CP2MO2(MU-CL)(MU-SME)(3)] - CRYSTAL-STRUCTURE OF (MU-SCH2CH2SH)(MU-SME)(3)]CENTER-DOT-0.5CH(2)CL(2)

Thermal reaction of the chloro-bridged complex [Cp2Mo2(mu-CL)(mu-SMe)( 3)] 1 with the dithiols HS(CH2)(n)SH (n = 2 or 3) affords the quadrupl y thio-bridged complexes [Cp2Mo2{mu-S(CH2)(n)SH}(mu-SMe)(3)] where n = 2 (2) or 3 (3). 2 has been shown by X-ray diffraction to contain the mu-eta(1)-dithiolate ligand S-(CH2)(2)SH which bridges an Mo-Mo single bond whose length is 2.606(1)Angstrom. The substitution reaction of t he chloro bridge in 1 also occurs with phenylphosphine, H2PPh, giving the mu-phosphido compound [Cp2Mo2(mu-HPPh)(mu-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 mu-chloro complex [Cp2Mo2(mu-Cl)(mu-PPh2)(mu-SMe)(2)] 5. All new products have been char acterized by spectroscopic analyses. (C) 1997 Elsevier Science S.A.