The kinetics and mechanism of the reaction of trico-ordinate phosphorus compounds with tetracyanoquinodimethane and tetracyanoethylene

被引:3
作者
Hall, CD
Beer, PD
Powell, RL
Naan, MP
机构
[1] Department of Chemistry, King's College London, Strand
来源
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS | 1995年 / 105卷 / 1-4期
关键词
tricoordinate phosphorus; tetracyanoquinodimethane; tetracyanoethylene; kinetics; mechanism;
D O I
10.1080/10426509508042057
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Trico-ordinate phosphorus compounds, ArnP(OPri)(3-n) where n = 0-3, react with tetracyanoquinodimethane (TCNQ) in acetonitrile in the presence of water to give the corresponding phosphoryl compounds, ArnP(O)(OPri)(3-n) and 1,4-bis-dicyanomethylbenzene (TCNQH(2)) in quantitative yield. The kinetics of these reactions are reported together with the Hammett rho-parameters from variation of substituents in the aryl group for n = 1, 2 and 3. On the basis of the available evidence, a mechanism is proposed involving one electron transfer from phosphorus (the donor) to TCNQ. A kinetic study of the reaction of triarylphosphines with TCNE in aqueous acetonitrile, however, suggests rate-limiting nucleophilic attack on nitrogen rather than the radical cation mechanism.
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页码:145 / 155
页数:11
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