N->P intramolecular stabilization of phosphenium ions and preparation of hypercoordinated phosphanes with unusual properties

被引：27

作者：

Carre, F ^{[1
]}

Chuit, C ^{[1
]}

Corriu, RJP ^{[1
]}

Mehdi, A ^{[1
]}

Reye, C ^{[1
]}

机构：

[1] UNIV MONTPELLIER 2,LAB PRECURSEURS ORGANOMET MAT,CNRS,UMR 5637,F-34095 MONTPELLIER 5,FRANCE

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1997年 / 529卷 / 1-2期

关键词：

stabilized phosphenium ions; hypercoordinated phosphane; pincer ligand; hexacoordinated phosphonium salt;

D O I：

10.1016/S0022-328X(96)06659-4

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction of ArLi 1 (Ar = [C6H3(CH2NMe2)(2)-2,6]) with Ph2PCl affords the phosphane 2 which, on treatment with HCl, gives rise to the monoprotonated ammonium salt 3, even in the presence of an excess of HCl. 2 reacts with Mel to give exclusively the phosphonium salt 4. Reaction of 1 with PhPCl2 gives the stabilized phosphenium ion [ArPPh]Cl-+(-) 6. This ion is reduced by LiAlH4 in ArPHPh 9, which undergoes hydride abstraction on treatment with trityl cation, giving the same ionic phosphorus species. This unusual reaction is an example of increased reactivity of a P-H bond resulting from hypercoordination at the phosphorus atom.

引用

页码：59 / 68

页数：10

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