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Nucleophilic Attack on Carbonyl Ligands in a Cyclooctatetraene (COT)-Coordinated Pentacarbonyl Diiron Complex. Isolation and Transformation of the Diiron Bridging Alkoxycarbyne Complexes [Fe2{μ-COC2H5}(COAr)(CO)38-C8H8)]

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journal contribution
posted on 02.01.2006, 00:00 by Shu Zhang, Lei Zhang, Qiang Xu, Jie Sun, Jiabi Chen
The reactions of pentacarbonyl(cyclooctatetraene)diiron, [Fe2(CO)58-C8H8)] (1), with aryllithium reagents, ArLi (Ar = C6H5, p-CH3C6H4, p-CF3C6H4), in ether at low temperature followed by alkylation with Et3OBF4 in aqueous or CH2Cl2 solution at low temperature gave the COT-coordinated diiron bridging alkoxycarbene complexes [Fe2{μ-C(OC2H5)Ar}(CO)48-C8H8)] (2, Ar = C6H5; 3, Ar = p-CH3C6H4; 4, Ar = p-CF3C6H4) and the novel COT-coordinated bridging alkoxycarbyne complexes [Fe2{μ-C(OC2H5)}(COAr)(CO)38-C8H8)] (5, Ar = C6H5; 6, Ar = p-CH3C6H4; 7, Ar = p-CF3C6H4) in 60−74% and 2−8% isolated yields, respectively. In solution complexes 57 were transformed into thermodynamically more stable complexes 24. The structure of 6 has been established by the X-ray diffraction studies.