Stable Mesoionic N-Heterocyclic Olefins (mNHOs)

被引：68

作者：

Hansmann, Max M. ^{[1
,2
]}

Antoni, Patrick W. ^{[2
]}

Pesch, Henner ^{[2
]}

机构：

[1] Tech Univ Dortmund, Fak Chem & Chem Biol, Otto Hahn Str 6, D-44227 Dortmund, Germany

[2] Georg August Univ Gottingen, Inst Organ & Biomol Chem, Tammannstr 2, D-37077 Gottingen, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 14期

关键词：

carbene homologues; main-group chemistry; N-heterocyclic olefins; ylides; 1,3-DIAZA-2-AZONIAALLENE SALTS; CATALYTIC-ACTIVITIES; PROTON AFFINITIES; CARBENES; COORDINATION; LIGANDS; ACTIVATION; COMPLEXES; CHEMISTRY; CYCLOADDITIONS;

D O I：

10.1002/anie.201914571

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report a new class of stable mesoionic N-heterocyclic olefins, featuring a highly polarized (strongly ylidic) double bond. The ground-state structure cannot be described through an uncharged mesomeric Lewis-structure, thereby structurally distinguishing them from traditional N-heterocyclic olefins (NHOs). mNHOs can easily be obtained through deprotonation of the corresponding methylated N,N '-diaryl-1,2,3-triazolium and N,N '-diaryl-imidazolium salts, respectively. In their reactivity, they represent strong sigma-donor ligands as shown by their coordination complexes of rhodium and boron. Their calculated proton affinities, their experimentally derived basicities (competition experiments), as well as donor abilities (Tolman electronic parameter; TEP) exceed the so far reported class of NHOs.

引用

页码：5782 / 5787

页数：6

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