Exploring the Limits of Frustrated Lewis Pair Chemistry with Alkynes: Detection of a System that Favors 1,1-Carboboration over Cooperative 1,2-P/B-Addition

被引：98

作者：

Chen, Chao ^{[1
]}

Eweiner, Florian ^{[1
,2
]}

Wibbeling, Birgit ^{[1
]}

Froehlich, Roland ^{[1
]}

Senda, Shunsuke ^{[2
]}

Ohki, Yasuhiro ^{[2
]}

Tatsumi, Kazuyuki ^{[2
]}

Grimme, Stefan ^{[1
]}

Kehr, Gerald ^{[1
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

[2] Nagoya Univ, Dept Chem, Fac Sci, Chikusa Ku, Nagoya, Aichi 4648602, Japan

来源：

CHEMISTRY-AN ASIAN JOURNAL | 2010年 / 5卷 / 10期

关键词：

alkynes; boron; carboboration; phosphorus; zirconocene; ZETA VALENCE QUALITY; AUXILIARY BASIS-SETS; DIHYDROGEN ACTIVATION; CRYSTAL-STRUCTURE; PI-COORDINATION; ORGANOBORATION; REACTIVITY; COMPLEXES; 1,1-ORGANOBORATION; POLYMERIZATION;

D O I：

10.1002/asia.201000189

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The zirconocene complex [{(C6F5)(2)B-(CH2)(3)-Cp}(Cp-PtBu2)ZrCl2] (6; Cp=cyclo-C5H4) was prepared by hydroboration of [(allyl-Cp)(CpPtBu2)ZrCl2] (5) with HB(C6F5)(2) ("Piers' borane"). It represents a frustrated Lewis pair (FLP) in which both the Lewis acid and the Lewis base were attached at the metallocene framework. Its reaction with 1-pentyne did not result in the 1,2-addition of or deprotonation reaction by the FLP, but rather in the 1,1-carboboration of the triple bond, thereby obtaining a ZIE mixture (1.2:1) of the respective organ-metallic substituted alkenes 7. The analogous reaction of 1-pentyne with the phosphorous-free system [{(C6F5)(2)B-(CH2)(3)-Cp))CpZrCl2] (9) gave the respective 1,1-carboboration products ((Z)-10/(E)-10 approximate to 1.3:1).

引用

页码：2199 / 2208

页数：10

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