Homogeneous Catalysis with AuIII: Insights into the Mechanism of the Alkoxylation of Alkynes

被引：1

作者：

Wong, Zhi Xiang ^{[1
]}

Lein, Matthias ^{[1
,2
]}

机构：

[1] Victoria Univ Wellington, Sch Chem & Phys Sci, Wellington, New Zealand

[2] Massey Univ Auckland, New Zealand Inst Adv Study, Ctr Theoret Chem & Phys CTCP, Auckland, New Zealand

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2015年 / 14期

关键词：

Homogeneous catalysis; Density functional calculations; Gold; Reaction mechanisms; Alkynes; CORRELATED MOLECULAR CALCULATIONS; POLARIZABLE CONTINUUM MODEL; GAUSSIAN-BASIS SETS; GOLD(I) COMPLEXES; HYDRATION; APPROXIMATION; ENERGY; ATOMS; GROUP-11; METHANOL;

D O I：

10.1002/ejic.201500152

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The mechanism of the Au-III-catalyzed nucleophilic addition of a small alkanol to an alkyne, which yields a ketal product, has been investigated computationally by using GGA (BP86), hybrid (PBE0) and double-hybrid (B2-PLYP-D3BJ) density functional theory with the large aug-cc-pVTZ (aug-cc-pVTZ-PP) basis sets of triple- quality. The importance of hydrogen-bonding networks is highlighted in the mechanism. The nucleophilic attacks possess relatively lower activation barriers than the hydrogen migrations, and the rate-determining step is predicted to be the last hydrogen migration step.

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收藏

页码：2381 / 2386

页数：6

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