One electron oxidation of chromium N,N-bis(diarylphosphino)amine and bis(diarylphosphino)methane complexes relevant to ethene trimerisation and tetramerisation

被引：79

作者：

School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, United Kingdom ^{[1
]}

机构：

[1] School of Chemistry, University of Bristol, Bristol, BS8 1TS, Cantock's Close

来源：

Dalton Trans. | 2007年 / 11卷 / 1160-1168期

关键词：

27;

D O I：

10.1039/b700559h

中图分类号：

学科分类号：

摘要：

Complexes of the type [(diphosphine)Cr(CO)4] (diphosphine = Ph2PN(iPr)PPh2, Ar2PN(Me)PAr2 or Ar2PCH2PAr2 (Ar = 2-C6H 4(MeO)) have been synthesised. In the solid state, these complexes show tight phosphine bite angles in the range 67.82(4)° to 71.52(5)° and the nitrogen atom in N,N-bis(diarylphophino)amine ligands adopts an almost planar (sp2) geometry. All of the complexes are readily oxidised electrochemically or chemically to corresponding Cr(i) species. There is no evidence for coordination of the pendant ether group in derivatives with Ar = 2-MeO-C6H4 in either Cr(0) or Cr(i) species. Treatment of the [(diphosphine)Cr(CO)4] complexes with [NO]BF4 yields [(diphosphine)Cr(NO)(CO)3]BF4. Removal of CO ligands to generate an oligomerisation-active species is not observed with amine oxides but triethyl aluminium is effective in this role, and active catalysts can be produced. The use of weakly coordinating anions seems crucial in achieving oligomerisation catalysis. © The Royal Society of Chemistry.

引用

页码：1160 / 1168

页数：8

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