Preparation and reactivity of nickel(0) complexes with η2-coordinated alkynylphosphines

被引：26

作者：

Bennett, MA ^{[1
]}

Castro, J ^{[1
]}

Edwards, AJ ^{[1
]}

Kopp, MR ^{[1
]}

Wenger, E ^{[1
]}

Willis, AC ^{[1
]}

机构：

[1] Australian Natl Univ, Res Sch Chem, Canberra, ACT 0200, Australia

来源：

ORGANOMETALLICS | 2001年 / 20卷 / 05期

关键词：

D O I：

10.1021/om000895o

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The eta (2)-alkynylphosphine complexes [Ni(eta (2)-Ph2PC=CR)(dcpe)] (R = Me(la) CO2Me(lb) Ph (Ic)), which are formed by displacement of ethylene from [Ni(C2H4)(dcpe)] by the corresponding alkynylphosphine, react with HCl (1 equiv) to give five-coordinate nickel(II) complexes, [NiCl{C(=CHR)PPh2-kappaP,C-1}(dcpe)] (R = Me (2a), CO2Me (2b), Ph (2c)), which contain a coordinated methylenephosphanickelacyclopropane fragment. In the case of la, the proton adds regiospecifically at the carbon atom bearing the methyl group. This mode of addition is favored for Ib,c, but small amounts of the addition products [NiCl{eta (1)-C(R)= CH(PPh2)}(dcpe)] (R = CO2Me (3b), Ph (3c)), arising from addition at the PPh2-bearing carbon atoms, are also formed. Unsaturated molecules such as CS2 and CO2 insert into the Ni-P bonds of complexes 2a,c to give five-membered nickelacycles. Complexes la, 2a,c, and 3c have been structurally characterized by X-ray diffraction analysis.

引用

页码：980 / 989

页数：10

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