一种用于水溶液中羰基硅氢化反应的掩蔽氢化亚铜催化剂。

A Masked Cuprous Hydride as a Catalyst for Carbonyl Hydrosilylation in Aqueous Solutions.

作者信息

Ritter Florian, Mukherjee Debabrata, Spaniol Thomas P, Hoffmann Alexander, Okuda Jun

机构信息

Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.

Current address: Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, 721302, India.

出版信息

Angew Chem Int Ed Engl. 2019 Feb 4;58(6):1818-1822. doi: 10.1002/anie.201811890. Epub 2019 Jan 3.

DOI:10.1002/anie.201811890

PMID:30536497

Abstract

Redox-unstable cuprous hydridotriphenylborate was isolated as an N-heterocyclic carbene adduct [(IPr)Cu(HBPh )] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with good thermal stability. Although this compound displays a contact ion-pair structure, Cu H-like catalytic activity was envisaged in carbonyl hydrosilylation. Sufficient moisture stability allowed the catalysis in aqueous/organic media. Mechanistic study further showed that a phenyl group on the borate anion is abstracted by [(IPr)Cu] to give the cationic organocopper complex [(IPr) Cu (μ-Ph)][BPh ].

摘要

氧化还原不稳定的氢化三苯基硼酸亚铜以具有良好热稳定性的N-杂环卡宾加合物[(IPr)Cu(HBPh₃)]（IPr = 1,3-双(2,6-二异丙基苯基)咪唑-2-亚基）形式被分离出来。尽管该化合物呈现出接触离子对结构，但在羰基氢化硅烷化反应中设想具有类似Cu-H的催化活性。足够的水分稳定性使得其能够在水/有机介质中进行催化反应。机理研究进一步表明，硼酸根阴离子上的一个苯基被[(IPr)Cu]夺取，生成阳离子有机铜配合物[(IPr)₂Cu(μ-Ph)][BPh₄]。