118013-31-3Relevant academic research and scientific papers
Reactions of triethylammonium salts of the [(μ-CO)(μ-RS)Fe2(CO)6]- anion with alkyl-, aryl-, and vinylmercuric halides. Formal C-alkylation of the bridging CO ligand
Seyferth, Dietmar,Archer, Colin M.,Ruschke, David P.,Cowie, Martin,Hilts, Robert W.
, p. 3363 - 3380 (2008/10/08)
The reaction of alkyl- and arylmercuric halides with [Et3NH][(μ-CO)(μ-RS)Fe2(CO)6] gives bridging acyl complexes, (μ-R′C=O)(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-σ,π-vinyl complexes, (μ-CH=CH2)(μ-RS)Fe2(CO)6 in the case of CH2=C-HHgBr. Methyl substituents on the vinyl carbon atoms stabilize the μ-acyl complex. The reaction of CH3OCH2CH2HgCl with [Et3NH][μ-CO)(μ-RS)Fe2(CO)6] gave the bridging carboxylato complex (μ-CH3CO2)(μ-RS)Fe2(CO)6. Such compounds are more readily prepared by the reaction of Hg(O2CR′)2 with [Et3NH][μ-CO)(μ-RS)Fe2(CO)6]. The reaction of Hg(SCH3)2 with [Et3NH][μ-CO)(μ-PhS)Fe2(CO)6] resulted in formation of (μ-CH3S) (μ-PhS)Fe2(CO)6. Possible mechanisms of these reactions are discussed. The structure of (μ-CH3CO2)(μ-t-BuS)Fe2(CO)6 has been determined by X-ray techniques. This compound crystallizes in the triclinic space group P1 with a = 13.608 (2) A?, b = 16.945 (1) A?, c = 8.599 (1) A?, α = 98.52 (1)°, β = 99.00 (1)°, γ = 113.03 (1)°, V = 1753.8 A?3, 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.
A simple route to hexacarbonyldiiron complexes containing a bridging thiolate and an organic bridging ligand by means of [(μ-RS)(μ-CO)Fe2(CO)6]- intermediates
Seyferth, Dietmar,Womack, Gary B.,Archer, Colin M.,Dewan, John C.
, p. 430 - 442 (2008/10/08)
The reaction of thiolate salts, M+SR-, with Fe3(CO)12 in THF at room temperature gives M[(μ-CO)-(μ-RS)Fe2(CO)6]. These react as nucleophiles at the oxygen of the bridging CO ligand (with Et3O+BF4-) and as nucleophiles at iron (with halides of potentially bridging groups: RC(O)Cl, Me2NC(S)Cl, allyl chloride, propargylic halides) to give products of type (μ-RS)(μ-organic group)Fe2(CO)6 in good yield. A less practical route to such products involves the action of 2 molar equiv of LiBEt3H on (μ-CH3CO)(μ-RS)Fe2(CO)6, followed by addition of the halide electrophile. The reaction of the [(μ-CO)(μ-RS)Fe2(CO)6]- anions with propargylic halides was shown to proceed by wav of an SN2′ mechanism. The structures of [Et3NH](μ-CO)(μ-mesitylS)Fe(CO)6], (μ-allyl)(μ-C2H5S)Fe2(CO)6, and (μ-allenyl)(μ-(CH3)3CS)Fe2(CO) 6 were determined by X-ray diffraction.
Novel C-alkylation of a CO-bridged dinuclear iron carbonyl anion: A new synthesis of Fe2(CO)6 complexes containing a bridging acyl ligand
Seyferth, Dietmar,Archer, Colin M.
, p. 2572 - 2574 (2008/10/08)
The reaction of anionic iron carbonyl complexes which contain a bridging CO ligand of type [Et3NH][(μ-CO)(μ-R′S)Fe2(CO)6] with alkyl- and arylmercuric halides, RHgX, gives products which contain a bridging acyl ligand in place of the bridging CO, (μ-RCO)(μ-R′S)Fe2(CO)6. With vinylic and alkynylmercurials, the bridging CO ligand is displaced and products of type (μ-σ,π-CH=CHR)(μ-R′S)Fe2(CO)6 and (μ-σ,π-C≡CR)(μ-R′S)Fe2(CO)6 are obtained. In contrast, reaction of [Et3NH][(μ-CO)(μ-R′S)Fe2(CO)6] with [Et3O][BF4] gives a bridging alkoxycarbyne complex, (μ-EtOC)(μ-R′S)Fe2-(CO)6.
