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Cleavage of Carbon−Sulfur Bonds by Triosmium Clusters. Evidence for a Novel Two-Center Mechanism Predicated on Metal−Metal Bond Cleavage

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journal contribution
posted on 10.05.2000, 00:00 by Richard D. Adams, O-Sung Kwon, Joseph L. Perrin
The 2-vinylthiacyclohexane cluster complex Os3(CO)10[μ-η3-S(CH2)4CHCHCH2] (1) is transformed into the complex Os3(CO)10[μ-η4-S(CH2)4CHCHCH2] (2) by a ring-opening cleavage of one carbon−sulfur bond, a CO ligand shift, and opening of the cluster. Compound 2 is converted into the complexes Os3(CO)10[μ-SCH2CH2CH2C(H)C(H)C(H)CH2](μ-H) (3) and Os3(CO)9[μ-η4-cis-S(CH2)4CHCHCH2] (4) by re-forming the metal−metal bond. Compound 4 isomerizes to Os3(CO)9[μ-η4-trans-S(CH2)4CHCHCH2] (5).