Browsing by Author "Seyferth, Dietmar"
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Item Reactions of 2-furyl, 2-thienyl, and N-methyl-2-pyrrolyl mercurials with [Et3NH][(.mu.-CO)(.mu.-RS)Fe2(CO)6] complexes. Synthesis of Fe2(CO)6 complexes with bridging .eta.1:.eta.2-furyl and thienyl ligands(1992) Seyferth, Dietmar; Anderson, Lea L.; Villafane, Fernando; Cowie, Martin; Hilts, RobertItem 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(1991) Seyferth, Dietmar; Archer, Colin M.; Ruschke, David P.; Cowie, Martin; Hilts, RobertThe 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.Item Synthesis and reactions of the [(.mu.-Ph2P)Fe2(CO)6]- anion(1992) Seyferth, Dietmar; Brewer, Karen S.; Wood, Timothy G.; Cowie, Martin; Hilts, RobertThe action of 2 molar equiv of LiBE^H on 0i-CH3C=O)0i-Ph2P)Fe2(CO)6 gives a reactive species which IR spectroscopic evidence suggests to be Li[(/i-Ph2P)Fe2(CO)6]. This species reacts with acid halides, RC(0)C1, Me2NC(S)Cl, Me2P(S)Cl, and chlorophosphines; neutral products of type 0t-E)0i-Ph2P)Fe2(CO)6 (E = RC=0, Me2NC=S, Me2P=S, R^) were obtained in good yield. Reaction with CS2 and RNCS gave anionic products, 0t-SC==S)0t-Ph2P)Fe2(CO)6 and Ot-RÑO=S)Ot-Ph2P)Fe2(CO)6. The [Oi-Ph2P)Fe2(CO)8]~ reagent is much more reactive than the known [^-CO)(p-Ph2P)Fe2(CO)6]~. The structure of (µCH3)2P==S)0t-PhS)Fe2(CO)6 (18b) has been determined by X-ray techniques. Compound 18b crystallizes in the orthorhombic space group P212121 with o = 12.494 (2) k,b- 17.075 (2) Á, c = 8.7909 (9) k,V1944.7 (7) Á3, and Z = 4. The two Fe(CO)3 groups in the complex are bridged by the benzenethiolate and the dimethylphosphino sulfide groups, the latter of which is S-bound to one metal and P-bound to the other. Within the SPMe2 ligand the P—S distance of 2.030 (2) A lies intermediate between that of a single (2.18 A) and a double (1.95 A) bond.