Structural changes accompanying the stepwise population of a B-C π bond

被引：66

作者：

Chiu, Ching-Wen ^{[1
]}

Gabbaie, Francois P. ^{[1
]}

机构：

[1] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2007年 / 46卷 / 36期

关键词：

boron; multiple bonds; NBO analysis; reduction;

D O I：

10.1002/anie.200702299

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Get Shorty: The central boron-carbon bond of an α-borylated carbocation undergoes a noticeable shortening upon reduction by one and two electrons, and the degree of twisting about this bond is also noticeably reduced (see graph). According to both experiment and theory, these effects result from the sequential population of the central boron-carbon π bond. (Graph Presented). © 2007 Wiley-VCH Verlag GmbH &. Co. KGaA.

引用

页码：6878 / 6881

页数：4

共 21 条

[1] X-RAY CRYSTAL-STRUCTURE OF THE BORON-STABILIZED CARBANION - [LI(12-CROWN-4)2][CH2C6H2(3,5-ME2)(4-B(2,4,6-ME3C6H2)2)].ET2O - EVIDENCE FOR BORON YLIDE CHARACTER [J].

BARTLETT, RA ;

POWER, PP .

ORGANOMETALLICS, 1986, 5 (09) :1916-1917

[2]

Chiu C.-W., 2007, ANGEW CHEM, V119, P1753

[3] A 9-borylated acridinyl radical [J].

Chiu, Ching-Wen ;

Gabbai, Francois P. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (10) :1723-1725

[4] Reactions of a borataalkene ligand at tantalocene centers:: Isonitrile insertion into the B-C bond of the [CH2B(C6F5)2] ligand via the η1 bonding mode [J].

Cook, KS ;

Piers, WE ;

Hayes, PG ;

Parvez, M .

ORGANOMETALLICS, 2002, 21 (12) :2422-2425

[5] Synthesis and chemistry of zwitterionic tantala-3-boratacyclopentenes: Olefin-like reactivity of a borataalkene ligand [J].

Cook, KS ;

Piers, WE ;

McDonald, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (19) :5411-5418

[6] Reactions of bis(pentafluorophenyl)borane with Cp2Ta(=CH2)CH3:: Generation and trapping of tantalocene borataalkene complexes [J].

Cook, KS ;

Piers, WE ;

Woo, TK ;

McDonald, R .

ORGANOMETALLICS, 2001, 20 (18) :3927-3937

[7] Electronic structure of pi-conjugated redox systems with borane/borataalkene end groups [J].

Fiedler, J ;

Zalis, S ;

Klein, A ;

Hornung, FM ;

Kaim, W .

INORGANIC CHEMISTRY, 1996, 35 (10) :3039-3043

[8]

Grigsby WJ, 1997, CHEM-EUR J, V3, P368

[9] Reactivity of the dimesityl-1,8-naphthalenediylborate anion:: isolation of the borataalkene isomer and synthesis of 1,8-diborylnaphthalenes [J].

Hoefelmeyer, JD ;

Solé, S ;

Gabbäi, FP .

DALTON TRANSACTIONS, 2004, (08) :1254-1258

[10]

Kaim W., 1984, ANGEW CHEM, V96, P611

← 1 2 3 →