Phosphorus and Olefin Substituent Effects on the Insertion Chemistry of Nickel(II) Hydride Complexes Containing Amido Diphosphine Ligands
作者:Lan-Chang Liang、Pin-Shu Chien、Pei-Ying Lee
DOI:10.1021/om701294a
日期:2008.7.1
A series of nickel(II) hydride complexes supported by amido diphosphine ligands, including symmetrical [N(o-C6H4PR2)2]− ([R-PNP]−; R = Ph, iPr, Cy) and unsymmetrical [N(o-C6H4PPh2)(o-C6H4PiPr2)]− ([Ph-PNP-iPr]−), have been prepared for the investigation of olefin insertion chemistry. The unsymmetrical ligand precursor H[Ph-PNP-iPr] (1d) that features different substituents (phenyl and isopropyl) at
酰胺基二膦配体支撑的一系列氢化镍(II)配合物,包括对称的[N(o -C 6 H 4 PR 2)2 ] -([R-PNP] -; R = Ph,i Pr,Cy)和不对称[N(o -C 6 H 4 PPh 2)(o -C 6 H 4 P i Pr 2)] -([Ph-PNP- i Pr] -),已准备好用于研究烯烃插入化学。制备了在两个磷供体上具有不同取代基(苯基和异丙基)的不对称配体前体H [Ph-PNP- i Pr](1d),其收率为53%,为无色晶体。用H [R-PNP](R = Ph(1a),i Pr(1b),Cy(1c))或1d处理Ni(COD)2(COD =环辛-1,5-二烯)产生相应的四种配位的氢化镍配合物2a - d。尝试分离2A导致代替到环辛-4-烯-1-基络合物[PH-PNP]镍(η 1 -C8 H 13)(3a)是COD插入2a的Ni-H键的结果。的反应图2a,d与乙烯