The Stabilizing Effects in Gold Carbene Complexes

被引：90

作者：

Comprido, Laura Nunes dos Santos ^{[1
]}

Klein, Johannes E. M. N. ^{[2
]}

Knizia, Gerald ^{[3
]}

Kaestner, Johannes ^{[2
]}

Hashmi, A. Stephen K. ^{[1
,4
]}

机构：

[1] Heidelberg Univ, Inst Organ Chem, D-69120 Heidelberg, Germany

[2] Univ Stuttgart, Inst Theoret Chem, Pfaffenwaldring 55, D-70569 Stuttgart, Germany

[3] Penn State Univ, Dept Chem, University Pk, PA 16802 USA

[4] King Abdulaziz Univ, Fac Sci, Dept Chem, Jeddah 21589, Saudi Arabia

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 35期

关键词：

alkenes; alkynes; carbene ligands; computational chemistry; gold; CATALYZED CYCLOISOMERIZATIONS; SKELETAL REARRANGEMENT; PLATINUM CATALYSIS; BASIS-SETS; 1,6-ENYNES; CARBONYL; CYCLIZATION; MECHANISMS; CHARACTER; REVEALS;

D O I：

10.1002/anie.201412401

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Bonding and stabilizing effects in gold carbene complexes are investigated by using Kohn-Sham density functional theory (DFT) and the intrinsic bond orbital (IBO) approach. The p-stabilizing effects of organic substituents at the carbene carbon atom coordinated to the gold atom are evaluated for a series of recently isolated and characterized complexes, as well as intermediates of prototypical 1,6-enyne cyclization reactions. The results indicate that these effects are of particular importance for gold complexes especially because of the low pi-backbonding contribution from the gold atom.

引用

页码：10336 / 10340

页数：5

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