N-Alkoxyimidazolylidines (NOHCs): nucleophilic carbenes based on an oxidized imidazolium core.
N-Alkoxyimidazolylidines (NOHCs): nucleophilic carbenes based on an oxidized imidazolium core.
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N-烷氧基咪唑基 (NOHC)：基于氧化咪唑鎓核心的亲核卡宾
DOI：
10.1039/d1cc05696d
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发表时间：
2022
影响因子：
4.9
通讯作者：
Peter R. Schreiner
中科院分区：
文献类型：
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作者：
Vladyslav V. Bakhonsky;Jonathan Becker;Grzegorz Mlostoń;Peter R. Schreiner
我们报道了 N-烷氧基咪唑亚基 (NOHC) 的首次制备，这是一种基于氧化咪唑鎓核的亲核卡宾。与常见的 NHC 相比，Arduengo 型类似卡宾中心显示出最大的上场 13C NMR 位移。所得卡宾金(I)配合物遵循13C NMR高场趋势，并显示出烷氧基取代基的显着影响。类似地，一系列NOHC-硒加合物的77Se和15N NMR位移显示与亲核试剂的键合中σ-供体增加和π-回供体减少。 NHC 家族的这一扩展为此类卡宾用作配体或催化剂提供了改变的电子特性。
We report the first preparation of N-alkoxyimidazolylidene (NOHC), a nucleophilic carbene based on an oxidized imidazolium core. The Arduengo-type analogous carbene center shows the most upfield 13C NMR shift compared to common NHCs. The obtained gold(I) complex of the carbene follows the 13C NMR upfield trend and shows the marked influence the alkoxy substituents. Similarly, the 77Se and 15N NMR shifts of a range of NOHC-selenium adducts show increased σ-donation and decreased π-back donation in the bonding with the nucleophile. This extension of the NHC family provides altered electronic properties for the use of such carbenes as ligands or catalysts.