Hevia, E and Perez, J and Riera, V (2002) Manganese(I) and rhenium(I) tricarbonyl (Alkylthio)methyl and alkylidenesulfonium complexes. Organometallics, 21 (24). pp. 5312-5319. ISSN 0276-7333Full text not available in this repository. (Request a copy from the Strathclyde author)
The reactions of Na[M(CO)(3)(bipy)] (M = Mn, Re) compounds with ClCH2SR (R = Me, Ph) afford the (alkylthio)alkyl complexes [Mn(CH2SMe)(CO)(3)(bipy)] (1a), [Mn(CH2SPh)(CO)(3)-(bipy)] (1b), [Re(CH2SMe)(CO)(3)(bipy)] (2a), and [Re(CH2SMe)(CO)(3)(bipy)] (2b). Methylation at sulfur of these compounds with methyl triflate affords the methylidenesulfonium cations [Mn(CH2SMe2)(CO)(3)(bipy)](+) (5a), [Mn(CH2SMePh)(CO)(3)(bipy)](+) (5b), [Re(CH2SMe2)(CO)(3)(bipy)](+) (6a), and [Re(CH2SMePh)(CO)(3)(bipy)](+) (6b) as their triflate salts. These new compounds were characterized by IR and NMR spectroscopy, and the crystal structures of 1b, 2a, 5b, and 6b have been determined by X-ray diffraction. The sulfonium complexes are unreactive toward PPh3 and pyridine. The reactions of 5b and 6b with I-, PPh2-, and SEt(-)anions afford the (phenylthio)methyl complexes 1b and 2b, resulting from nucleophilic attack at the methyl group. 5b and 6b react with styrene to give phenylcyclopropane, free thioanisole, and the corresponding [M(OTf)(CO)(3)(bipy)] complex.
|Keywords:||metal carbene complexes, phase-transfer-catalysis, crystal structures, methylene transfer, reagents, cyclopropanation, ligands, photochemistry, Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Inorganic Chemistry|
|Subjects:||Science > Chemistry|
|Department:||Faculty of Science > Pure and Applied Chemistry|
|Depositing user:||Pure Administrator|
|Date Deposited:||21 Oct 2011 11:34|
|Last modified:||04 May 2016 20:15|