Activation of hydrogen by cationic cyclopentadienylmolybdenum dimers with sulfido ligands. 2. Cationic complexes derived from reactions with vinyl halides

摘要: The reaction of (CpMo-..mu..-S)/sub 2/S/sub 2/CH/sub 2/ (Cp = C/sub 5/H/sub 5/) with ..beta..-bromostyrene results in the formation a ..beta..-phenyl-alkenylthiolate bridged cationic complex ((CpMo)/sub 2/(S/sub 2/)(..mu..-S)(..mu..-SC(H)C(H)Ph))Br, I. product has been characterized by spectral methods and an X-ray diffraction study. I crystallized space group P2/sub 1//c 13.325 (2) A, b 15.868 (7) c 25.901 (11) ..beta.. 98.30 (3)/sup 0/. trans-vinylthiolate ligand is oriented equatorial configuration away from sulfido dimer. Complex reacts reducing agents to form mixed valence molybdenum(III)/molybdenum(IV) derivative which rapidly disproportionates new molybdenum(III) dimer two vinylthiolate ligands formula (CpMo)/sub 2/)(..mu..-SCHC(H)Ph)/sub 2/, III. hydrogen at 40/sup 0/C ethylbenzene 2/. Intermediates this hydrogenolysis have detected NMR synthesized alternate routes. They include cation 2/)(..mu..-S)(..mu..-SC(H)(Me)Ph))Br, IV, neutral 2/)(..mu..-SCH(Me)Ph)/sub V. Possible pathways for these intermediates are discussed.