NMRテクニックの有機金属化合物への応用

概要

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Application of NMR techniques, especially a spin saturation transfer technique, to several organometallic compounds are reported with emphasis on compounds undergoing fluxional behavior with two-electron-threecentered bonds such as a M-H-C bond, i.e. agostic interaction, and a M-H-H bond, i.e. a molecular hydrogen ligand. 13C spin saturation transfer experiments on the tautomers of H2Os3(CO)10(μ-CH2) and HOs(CO)10(μ-CH3) show intramolecular hydrogen exchange to convert all of the four isomers. 1H spin saturation tranfer experiments on [RuH(diop)2] PF6 show intramolecular hydrogen exchange between the hydride ligand and an aliphatic proton, presumably involving an agostic interaction, of the phosphine ligand. 1H spin saturation transfer experiments on [RuH(η2-H2)(dppp)2]PF6 show intramolecular hydrogen exchange between the molecular hydrogen and the hydride ligand. Application of isotopic perturbation of resonance to agostic interaction is mentioned as a method to show the presence of a proton of an agostic interaction undergoing a rapid exchange.
社団法人有機合成化学協会の論文