UNUSUALLY LEWIS BASIC PRO-AZAPHOSPHATRANES

被引：49

作者：

LARAMAY, MAH ^{[1
]}

VERKADE, JG ^{[1
]}

机构：

[1] IOWA STATE UNIV,DEPT CHEM,GILMAN HALL,AMES,IA 50010

来源：

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 1991年 / 605卷 / 14期

关键词：

AZAPHOSPHATRANES; LEWIS BASICITY OF PRO-AZAPHOSPHATRANES; P-31; NMR;

D O I：

10.1002/zaac.19916050120

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The title compounds of the type P(RNCH2CH2)3N (1, R = H; 2, R = Me; 3, R = CH2Ph) display the unexpected basicity trend 1 > 2 > 3 with respect to protonation which forms the azaphosphatranes H activated P(RNCH2CH2)3N+ (4, R = H; 5, R = Me; 6, R = CH2Ph). The unusual basicity order 1 > 2 > 3 is also supported by the trend in 1J(PSe) values obtained for SeP(RNCH2CH2)3N (8, R = H; 9, R = CH2Ph; 10, R = Me). Deprotonation of 4 is shown to produce a variety of deprotonated derivatives which were trapped by alkylation with MeI. A favored rationale for the unusual weakness of 4 as a protonic acid (pKa in DMSO, 29.6) is an unusual stability of the axial three-center four-electron bond signalled by the unusually high field P-31 chemical shift of this cation (-42 ppm).

引用

页码：163 / 174

页数：12

共 32 条

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