Oxidative addition of thiols, disulfides, iodine, and hydrogen iodide to W(CO){sub 3}(P{sup i}Pr{sub 3}){sub 2}. Preparation of stable 17-electron tungsten thiolate radicals from complexes with weak W-H bonds
- Univ. of Miami, Coral Gables, FL (United States)
In an attempt to extend the radical series W(CO){sub 3}(P{sup i}P{sub 3}){sub 2}(X) to include X = H, the interaction of chromium radicals with the molecular hydrogen complex was investigated. This reaction was studied under 60 atm of H{sub 2} in THF solution. No sign of interaction between the chromium radical and either the molecular hydrogen complex or its dihydride tautomer was observed. We conclude that this reaction does not occur since the first bond dissociation energy of W(CO){sub 3}(P{sup i}Pr{sub 3}){sub 2}(H){sub 2} is much higher than that for W(CO){sub 3}(P{sup i}Pr{sub 3}){sub 2}(H)(SPh). The low W-H bond strengths in the thiolate derivative may be due in part to stabilization of the 17-electron radical via lone pair donation from sulfur to tungsten. In spite of the failure of the chromium radical to abstract one H atom from the molecular hydrogen complex as shown, phenyl disulfide reacts under hydrogen pressure with net transfer of two hydrogen atoms. Production of up to 2 mol of thiophenol and the tungsten thiolate radical in the approximate stoichiometry occurs rapidly on mixing. This represents the first example of a hydrogen transfer reaction (other than H/D exchange) for W(CO){sub 3}(P{sup i}Pr{sub 3}){sub 2}(H{sub 2}). The mechanism of this reaction is unknown. 16 refs., 1 fig.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 102769
- Journal Information:
- Journal of the American Chemical Society, Vol. 116, Issue 17; Other Information: PBD: 24 Aug 1994
- Country of Publication:
- United States
- Language:
- English
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