111237-51-5Relevant academic research and scientific papers
Reactions of bimetallic complexes. 4. Ligand transfer reactions between different metallic sites. Synthesis, characterization, and reactivity of acetylenic cluster and dimeric complexes of cobalt and iron. Crystal structures of [(η5-C5H5)Fe(CO){μ-SMeCH=C(CF 3)}]2 and [(CO)3Co(μ-CF ...
Rumin, René,Manojlovi?-Muir, Ljubica,Muir, Kenneth W.,Pétillon, Francois Y.
, p. 375 - 383 (2008/10/08)
Full title: Reactions of bimetallic complexes. 4. Ligand transfer reactions between different metallic sites. Synthesis, characterization, and reactivity of acetylenic cluster and dimeric complexes of cobalt and iron. Crystal structures of [(η5-C5H5)Fe(CO){μ-SMeCH=C(CF 3)}]2 and [(CO)3Co(μ-CF3C2CF3)Co(CO) 2{(SMe)Fe(η5-C5H5)(CO) 2}]. Photolysis of the acyl-iron complex [Cp(CO)FeC(O)C(CF3)C(R)SMe] (1, R = H, CF3; Cp = η5-C5H5) gave [Cp(CO)Fe{μ-C(CF3)=C(R)(SMe)}2Fe(CO)Cp] (2) in almost quantitative yield. X-ray analysis of 2 (R = H) reveals that the dimeric structure is based on a tub-shaped Fe2S2C4 ring. The complex crystallizes in the space group Pbca, with a = 15.068 (4) A?, b = 18.649 (3) A?, c = 16.092 (3) A?, and Z = 8. R = 0.029 for refinement of 289 parameters with 3975 unique observations. Thermal reaction of 2 with Co2(CO)8 in toluene afforded the new tetracobalt cluster [Cp2Co4(CO)4(μ-CO)(μ-CF3C 2CF3)] (3) and the dinuclear derivative [(C6H5Me)Co(μ-CF3C2CF 3)Co(CO)3] (4); formation of these compounds implies that an exchange of ligands (hexafluorobut-2-yne, cyclopentadienyl, or carbonyl) took place. In 3 the alkyne is incorporated into a closo-Co4C2 cluster framework. Exchange of ligands is also observed when the dinuclear complexes [(CO)3Co(μ-CF3C2CF3)Co(CO) 3] and [Cp(CO)Fe(μ-SMe)2Fe(CO)Cp] react in refluxing toluene to give the new isomers cis- and trans-[Cp(CO)2FeC(CF3)=C(CF3)Me] in addition to 3 and 4. At lower temperatures (50-90°C) the same reactants produced a new trinuclear derivative, [(CO)3Co(μ-CF3C2CF3)Co(CO) 2{(SMe)Fe(CO)2Cp}] (8), shown by X-ray analysis to be derived by substitution of [CpFe(CO)2(SMe)] for an axial CO ligand of [(CO)3Co(μ-CF3C2CF3)Co(CO) 3]. 8 crystallizes in the space group Cc, with a = 13.978 (2) A?, b = 13.948 (3) A?, c = 23.221 (4) A?, β = 97.74 (1)°, and Z = 8. R = 0.045 for refinement of 336 parameters with 1663 observations.
