Reactions of triethylammonium salts of the [(.mu.-CO)(.mu.-RS)Fe2(CO)6]- anion with alkyl-, aryl-, and vinylmercuric halides. Formal C-alkylation of the bridging CO ligand
The reaction of alkyl- and arylmercuric halides with [Et3NH][(µ-CO)(p-RS)Fe2(CO)6] gives bridging acyl complexes, (p-R'C=0)(µ-RS)Fe2(CO)6. In the case of vinylmercuric halides the bridging acyl complexes are less stable and, in some cases (CH2=CHHgBr, PhCH=CHHgCl, ClCH=CHHgCl), they undergo decarbonylation to give the µ- , -vinyl complexes, (p-CH=CH2)(p-RS)Fe2(CO)6 in the case of CH2=CHHgBr. Methyl substituents on the vinyl carbon atoms stabilize the µ-acyl complex. The reaction of CH3OCH2CH2HgCl with [Et^NH] [µ-CO) (p-RS)Fe2(CO)g] gave the bridging carboxylato complex (µCH3C02)(p-RS)Fe2(C0)e. Such compounds are more readily prepared by the reaction of Hg(02CR')3 with [ 3 ][(µ-00)(µ- 8) ß2(00)6]. The reaction of Hg(SCH3)2 witii [Et3NH][Oi-CO)(p-PhS)Fe2(CO)6] resulted in formation of (p-CH3S)(p-PhS)Fe2(CO)6. Possible mechanisms of these reactions are discussed. The structure of (p-CH3C02)(p-t-Bu8)Fe2(C0)6 has been determined by X-ray techniques. This compound crystallizes in the triclinic space group Pi with a = 13.608 (2) Á, b = 16.945 (1) Á, c = 8.599 (1) A, a = 98.52 (1)°, ß = 99.00 (1)°, y = 113.03 (1)°, V = 1753.8 Á3, and Z = 4. Refinement has converged at R = 0.055 and Rw = 0.093 on the basis of 325 parameters varied and 3310 unique observations. Both independent molecules have essentially identical geometries in which the Fe2(CO)6 moiety is bridged by a 1,1-dimethylethanethiolate and an acetate ligand.
Dietmar Seyferth, Colin M. Archer, David P. Ruschke, Martin Cowie, and Robert W. Hilts. Reactions of triethylammonium salts of the [(.mu.-CO)(.mu.-RS)Fe2(CO)6]- anion with alkyl-, aryl-, and vinylmercuric halides. Formal C-alkylation of the bridging CO ligand. Organometallics 1991 10 (9), 3363-3380. DOI: 10.1021/om00055a062
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