Disilametallacycles as a Platform for Stabilizing M(II) and M(IV) (M = Fe, Ru) Centers: Synthesis and Characterization of Half-Sandwich Complexes and Their Application to Catalytic Double Silylation of Alkenes and Alkynes
作者:Yusuke Sunada、Tsuyoshi Imaoka、Hideo Nagashima
DOI:10.1021/om3012322
日期:2013.4.8
A series of group 8 half-sandwich disilametallacycles, (eta(6)-arene)M-II(Me2SiC6H4SiMe2)L and (eta(6)-arene)M-IV(H)(2)(Me2SiC6H4SiMe2) (M = Fe, Ru) in the formal oxidation states of M(II) and M(IV) were synthesized and characterized. Both the M(II) and the M(IV) oxidation states were effectively stabilized by the disilametallacycle skeleton, and facile interconversion between (eta(6)-arene)M-II-dinitrogen, (eta(6)-arene)M-II-carbonyl, and (eta(6)-arene)M-IV-dihydride complexes bearing a disilaferracycle framework was accomplished. These M(II) and M(IV) complexes can easily generate coordinatively unsaturated 16e disilametallacycles, (eta(6)-arene)M-II(Me2SiC6H4SiMe2), by dissociation of L or H-2, and stoichiometric and/or catalytic double silylation of alkenes and alkynes was realized thorough this 16e intermediate.
Half-Sandwich (η<sup>6</sup>-Arene)iron(II) Dinitrogen Complexes Bearing a Disilaferracycle Skeleton as a Precursor for Double Silylation of Ethylene and Alkynes
作者:Yusuke Sunada、Tsuyoshi Imaoka、Hideo Nagashima
DOI:10.1021/om100889w
日期:2010.12.13
solvent under a nitrogen atmosphere afforded the dinuclear bis(silyl)iron complexes [(η6-arene)Fe(Me2SiC6H4SiMe2)]2(μ-η1:η1-N2) (1), which have an end-on-bound bridging dinitrogen ligand. The dinitrogen unit easily dissociated from the Fe center to generate the mononuclear (η6-arene)FeII(Si)2L or (η6-arene)FeIV(Si)2H2 complexes by the reactions with CO, PPh3, and H2.