118772-52-4Relevant academic research and scientific papers
Reactions of di- and polynuclear complexes. 6. 1 Reaction of [(η5-C5H5)(CO)Fe{μ-C(CF 3)=C(CF3)SMe}2Fe(CO)(η5-C 5H5)] with [Fe3(CO)12]. Ligand exchange between metals: Synthesis and characterization of di- and trinuclear iron-alkyne complexes. ...
Rumin, René,Petillon, Fran?ois,Manojlovi?-Muir, Ljubica,Muir, Kenneth W.
, p. 944 - 952 (2008/10/08)
Full title: Reactions of di- and polynuclear complexes. 6. 1 Reaction of [(η5-C5H5)(CO)Fe{μ-C(CF 3)=C(CF3)SMe}2Fe(CO)(η5-C 5H5)] with [Fe3(CO)12]. Ligand exchange between metals: Synthesis and characterization of di- and trinuclear iron-alkyne complexes. Crystal structure of [{Fe(CO)3}2{μ-(CF3)CCC[Fe(η 5-C5H5)(CO)2]}]. The dinuclear complex [Cp(CO)Fe{μ-(CF3)C=C(CF3)SMe}2Fe(CO)Cp] (1) reacts in toluene with [Fe3(CO)12] to form a chromatographically separable mixture of two cluster compounds, [{Fe(CO)3}2{μ-(CF3)C2(CF 3)S}] (2) and [Fe3Cp2(CO)3(μ 3-CO)(μ-CO)(μ3-CF3C2CF 3)] (6), together with the di- and trinuclear species {Fe(CO)3}2{C3F2(CF3)SMe} (3), {Fe(CO)3}2(μ-SMe){μ-C(CF3)=C(CF 3)H} (4), and {Fe(CO)3}2{μ-(CF3)C 3[FeCp(CO)2]} (5). Cluster 6 is obtained as a mixture of two isomers, 6a and 6b. The same reactants in benzene yield a similar mixture, except that 5 is absent and two isomeric iron dinuclear species [Cp(CO)Fe{μ-(CF3)C2(CF3)SMe}Fe(CO) 3] (7a,b) are also obtained. Heating 1 and Fe3(CO)12 in tetrahydrofuran gives 7a, 7b, and yet a third isomer, 7c. On being heated in toluene, the isomeric complexes 7a and 7c decompose to [CpFe(μ-CO)2(μ-CF3C2CF3)FeCp] (8). The formation of these derivatives implies ligand-exchange processes between different metal sites. The molecular structures of compounds 2 and 6a have been established by single-crystal X-ray diffraction studies, which were communicated elsewhere. 6a contains a triangulo Fe3 unit μ3 bridged by CO; one of the Fe-Fe edges is semibridged by a second CO ligand, and the remaining CO ligands are terminally bonded to a single iron atom. The CF3C2CF3 alkyne ligands in 6a and 6b each adopt μ3-η2-∥ bonding modes but differ in their orientations with respect to the unsymmetrically substituted Fe3 triangles. Compound 2 has also been shown to contain a μ3-η2-∥-CF3C2CF 3 unit bridging an Fe2S triangle. X-ray analysis of 5 reveals the presence of a new ligand, (CF3)CC= CFeCp(CO)2, which bridges two Fe(CO)3 units. This new ligand results from abstraction of three fluorine atoms from a CF3 group. The Fe(CO)3 units are also linked by an Fe-Fe bond of 2.477 (2) A?. 5 crystallizes in the orthorhombic space group Pbca with a = 13.533 (4), b = 14.748 (4), c = 20.067 (3) A?, and R = 0.041 for refinement of 280 parameters from 2619 unique observations. The molecular structures of the isomers 7, isomer 6b, and compounds 4 and 8 have been assigned from consideration of their infrared, mass, and NMR spectra (1H, 19F, and 13C{1H}). The catalytic activity of the trinuclear species 6 in the homogeneous isomerization of straight-chain alkenes is described.
