Acetylene/Vinylidene Rearrangements of Fe(CO)2L2(silylacetylene) Complexes (L=Phosphorus Donor)
作者:Christine Gauss、Dario Veghini、Heinz Berke
DOI:10.1002/cber.19971300208
日期:1997.2
products Fe(CO)2L2(H)(C≡CSiMe3) [L PEt3, 3a; L P(OiPr)3, 3c]. The presence of a small amount of Al2O3 in hexane irreversibly converts 3a and 3c into the vinylidene compounds Fe(CO)2L2CC(H)SiMe3[L PEt3, 4a; L P(OiPr)3, 4c]. The chromatographic work-up of 4c additionally leads to the hydrolysis product Fe(CO)2[P(OiPr3)2]2CCH2 (2d). The reaction of the phosphite-substituted derivative Fe(CO)2[P(OMe)3]2I-
Fe(CO)2(PEt 3)2 N 2(1a)和[Fe-(CO)2(PEt 3)2 ] 2 N 2(1b)的混合物与乙炔的反应生成三种络合物:Fe( CO)2(PEt 3)2(π-HC≡CH)(2a),Fe(CO)2(PEt 3)2(H)(C≡CH)(2b)和Fe(CO)2(PEt 3)2 CCH 2(2c中)。在甲硅烷基化的硅胶上色谱分离后,将2a-c的混合物完全转化为2c。的类似反应1A,B或Fe的(CO)2 [P(O我PR)3 ] 2 Ñ 2(1D)与HC≡CSiMe 3,得到初级氧化加成产物的Fe(CO)2大号2(H) (C≡CSiMe 3)[L PET 3,图3a ; LP(O我PR)3,图3c ]。少量Al 2 O 3的存在在己烷中不可逆地转化3A和图3c到亚乙烯基化合物的Fe(CO)2大号2 CC(H)森达3 [L PET 3,图4a ; LP(O我PR)3,4C ]。4c的色谱处理还会产生水解产物Fe(CO)2