Cyclic metal(oid) clusters control platinum-catalysed hydrosilylation reactions: from soluble to zeolite and MOF catalysts

被引：23

作者：

Rivero-Crespo, Miguel ^{[1
,5
]}

Oliver-Meseguer, Judit ^{[1
]}

Kaplonska, Klaudia ^{[2
]}

Kustrowski, Piotr ^{[2
]}

Pardo, Emilio ^{[3
]}

Pedro Ceron-Carrasco, Jose ^{[4
]}

Leyva-Perez, Antonio ^{[1
]}

机构：

[1] Univ Politecn Valencia, CSIC, Inst Tecnol Quim, Avda Naranjos S-N, Valencia 46022, Spain

[2] Jagiellonian Univ, Fac Chem, Gronostajowa 2, PL-30387 Krakow, Poland

[3] Univ Valencia, Inst Ciencia Mol ICMol, Valencia 46980, Spain

[4] Univ Catolica Murcia UCAM, Reconocimiento & Encapsulac Mol REM, Murcia, Spain

[5] Swiss Fed Inst Technol, Swiss Fed Inst Technol, Dept Chem & Appl Biosci, Vladimir Prelog Weg 1-5-10, CH-8093 Zurich, Switzerland

来源：

CHEMICAL SCIENCE | 2020年 / 11卷 / 31期

基金：

欧洲研究理事会;

关键词：

SELECTIVE HYDROSILYLATION; ALKYNES; COMPLEXES; EFFICIENT; LIGAND; BOND; HYDROGEN; REGIOSELECTIVITY; NANOPARTICLES; MECHANISM;

D O I：

10.1039/d0sc02391d

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Pt-catalysed addition of silanes to functional groups such as alkenes, alkynes, carbonyls and alcohols, i.e. the hydrosilylation reaction, is a fundamental transformation in industrial and academic chemistry, often claimed as the most important application of Pt catalysts in solution. However, the exact nature of the Pt active species and its mechanism of action is not well understood yet, particularly regarding regioselectivity. Here, experimental and computational studies together with an ad hoc graphical method show that the hydroaddition of alkynes proceeds through Pt-Si-H clusters of 3-5 atoms (metal(oid) association) in parts per million amounts (ppm), which decrease the energy of the transition state and direct the regioselectivity of the reaction. Based on these findings, new extremely-active (ppm) microporous solid catalysts for the hydrosilylation of alkynes, alkenes and alcohols have been developed, paving the way for more environmentally-benign industrial applications.

引用

页码：8113 / 8124

页数：12