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.