Dihalogeno(diphosphane)metal(<scp>ii</scp>) complexes (metal = Co, Ni, Pd) as pre-catalysts for the vinyl/addition polymerization of norbornene – elucidation of the activation process with B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>/AlEt<sub>3</sub>or Ag[closo-1-CB<sub>11</sub>H<sub>12</sub>] and evidence for the in situ formation of “naked” Pd<sup>2+</sup>as a highly active species
作者:Paul-Gerhard Lassahn、Vasile Lozan、Biao Wu、Andrew S. Weller、Christoph Janiak
DOI:10.1039/b302937a
日期:——
(AlEt3). The nickel(II) and palladium(II) complexes show very high polymerization activities up to 107 gpolymer molmetal−1 h−1. Yet, the complexes Pd(dppe)Cl2 (5, 1.9 × 107 gpolymer molPd−1 h−1) and Pd(dppp)Cl2 (6, 3.0 × 103 gpolymer molPd−1 h−1) demonstrated that small changes in the ligand structure could have great effects on the polymerization activity [dppe = 1,2-bis(diphenylphosphino)ethane, Ph2P(CH2)2PPh2;
二卤代金属(II)与二齿膦的络合物配体一般类型[M Ph 2 P(CH 2)n PPh 2 } X 2 ]具有n = 2至5,X = Cl或Br,M = Co,Ni或Pd催化剂 为了 乙烯基塑料/的加成聚合 降冰片烯。这些络合物可以用路易斯酸甲基铝氧烷(MAO)或三(五氟苯基)硼烷,B(C 6 F 5)3与三乙基铝(方法3)。镍(II)和钯(II)配合物显示出很高的聚合活性高达10 7 g聚合物mol金属-1 h -1。然而,复合物的Pd(DPPE)氯2 (5,1.9×10 7克聚合物摩尔钯-1 ħ -1)和Pd(DPPP)氯2 (6,3.0×10 3克聚合物摩尔钯-1 ħ -1)表明配体 结构可能对聚合活性有很大影响[dppe = 1,2-双(二苯基膦基)乙烷,Ph 2 P(CH 2)2 PPh 2;dppp =1,3-双(二苯基膦基)丙烷,Ph 2 P(CH 2)3 PPh 2 ]。预激活的过程催化剂