Reactions of electrophiles with a metal-hydride complex. Reduction of CS{sub 2} by Cp*Rh(PMe{sub 3})H{sub 2} to produce the bridging methanedithiolate complex Cp*Rh(PMe{sub 3})(SCH{sub 2}S)
- Univ. of Rochester, NY (United States)
The title complex Cp*Rh(PMe{sub 3})(SCH{sub 2}S) (3) was prepared by the reaction of Cp*Rh(PMe{sub 3})H{sub 2} with Cs{sub 2}. No reaction was observed with CO{sub 2} at ambient or elevated temperatures and pressures. Reaction with OCS gave the known compounds Cp*Rh(PMe{sub 3})(CO) (4) and Cp*Rh(CO){sub 2} (5) plus S{double_bond}PMe{sub 3}. Kinetic measurements show a first-order dependence on [CS{sub 2}] and a small dependence on solvent polarity. Activation parameters for the reaction with CS{sub 2} were also measured, consistent with an associative transition state. The molecular structure of 3 was determined by a single-crystal X-ray diffraction study. 3 crystallizes in the monoclinic space group P2{sub 1}/n with a = 8.594 (5) {Angstrom}, b = 21.546 (7) {Angstrom}, c = 9.050 (4) {Angstrom}, {beta} = 95.73 (4){degrees}, and Z = 4. 13 refs., 3 figs., 4 tabs.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG02-86ER13569
- OSTI ID:
- 555008
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 2 Vol. 11; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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