Nucleophilic ring opening of a bridging thietane ligand in n open tetraosmium carbonyl cluster complex
- Univ. of South Carolina, Columbia, SC (United States)
The complex Os{sub 4}(CO){sub 12}({mu}-CO)[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}] (1) was found to react with bis(triphenylphosphine)nitrogen(1+) chloride, [PPN]Cl, at 25 {degrees}C to yield the salt [PPN][Os{sub 4}({mu}-CO)(CO){sub 12}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}Cl)] (2;43%), in which the chloride ion was added to one of the methylene groups of the SCH{sub 2}CMe{sub 2}CH{sub 2} ligand in a ring-opening process that involved the cleavage of one of the carbon-sulfur bonds. Compound 2 was converted to the neutral complex Os{sub 4}(CO){sub 13}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}Cl)({mu}-H) (3) by protonation with HCl. Complex 3 was characterized crystallographically and was found to contain a 4-chloro-3,3-dimethylpropanethiolato ligand bridging the wing-tip metal atoms of a butterfly tetrahedron of four metal atoms in the cluster. A hydride ligand bridges one of the edge metal-metal bonds of the cluster. Compound 3 was obtained in good yield (67%) in one step by the reaction of 1 with HCl. At 97 {degrees}C, 3 was decarbonylated to form the complex Os{sub 4}(CO){sub 12}({mu}{sub 3}-SCH{sub 2}CMe{sub 2}CH{sub 2}Cl)({mu}-H) (4;97%). Compound 4 was also characterized crystallographically and was found to contain a triply bridging 4-chloro-3,3-dimethylpropanethiolato ligand serving as a 5-electron donor. Data for 1: space group = P1, a = 10.205 (4) {Angstrom}, b = 14.399 (2) {Angstrom}, c = 9.342 (2) {Angstrom}, {alpha} = 20.646 (4) {Angstrom}, b = 9.610 (1) {Angstrom}, c = 8.753 (1) {Angstrom}, {alpha} = 116.308 (9){degrees}, {beta} = 102.27 (2){degrees}, {gamma} = 75.12 (1){degrees}, Z = 2, 3186 reflections, R = 0.032. Data for 4: space group = P1, a = 10.558 (1) {Angstrom}, b = 13.673 (2) {Angstrom}, c = 9.473 (1) {Angstrom}, {alpha} = 94.10 (1){degrees}, {beta} = 91.424 (9){degrees}, {gamma} = 76.08 (1){degrees}, Z = 2, 2421 reflections, R = 0.036. 14 refs., 3 figs., 10 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 554996
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 9 Vol. 11; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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