Transformations of 3,3-dimethylthietane in triosmium cluster complexes
- Univ. of South Carolina, Columbia, SC (United States)
Three products were isolated from the thermolysis of either Os{sub 3}(CO){sub 11}[SCH{sub 2}CMe{sub 2}CH{sub 2}] (1) or Os{sub 3}-(CO){sub 10}[{mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}] (2) at 97{degree}C. These were identified on the basis of IR and {sup 1}H NMR spectroscopy and single-crystal X-ray diffraction analyses as Os{sub 2}(CO){sub 6}[{mu}-SCH{sub 2}C(Me)CH{sub 2}(CH{sub 2})]({mu}-H) (3; 14%, 18%), Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}C(Me){sub 2}CH]({mu}-H) (4; 18%, 21%) and Os{sub 4}(CO){sub 12}({mu}-CO)[{mu}-SCH{sub 2}CH{sub 2}] (5; 8%, 12%). Treatment of 4 with H{sub 2}/CO (1200 psi, 5/1) at 97{degree}C yielded 3 (47%) and Os{sub 3}(CO){sub 10}[{mu}-SCH{sub 2}CMe{sub 3}]({mu}-H) (23%). When subjected to UV irradiation, 1 and 2 were converted to the metallacyclic isomer Os{sub 3}-(CO){sub 10}[{mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}] (6) in 30% and 47% yields, respectively. Thermolysis of 6 at 97{degree}C produced 3 and 4. Compound 6 was carbonylated (500 psi) at 70{degree}C to yield Os{sub 3}(CO){sub 11}[{mu}-SCH{sub 2}C(Me){sub 2}CH{sub 2}] (7; 11%) and Os{sub 3}(CO){sub 11}[{mu}-SCH{sub 2}C(Me){sub 2}CH{sub 2}C=O] (8; 42%), which is formed by a CO insertion into the metal-carbon bond of the metallacycle. Compound 6 reacts with [(Et){sub 4}N]{sup +}Cl{sup {minus}} at 25{degree}C to form [Os{sub 3}(CO){sub 9}({mu}-SCH{sub 2}C-(Me){sub 2}CH{sub 2})({mu}-Cl)]-[(Et){sub 4}N]{sup +} (9; 87%) by decarbonylation and addition of Cl{sup {minus}} to the cluster. Complexes 7-9 were also characterized by single-crystal X-ray diffraction analyses. All three compounds contain open clusters of the three metal atoms in which the sulfur atom bridges the pair of metal atoms that are not mutually bonded. Compound 8 contains a thiametallacyclohexanone ring formed by the insertion of a CO group into the metal-carbon bond of the metallacycle in 7. Compound 9 was formed by the cluster-opening addition of chloride to 6 and contains a bridging chloro ligand. 16 refs., 5 figs., 16 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 458725
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 6 Vol. 11; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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