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A Cationic Zinc Hydride Cluster Stabilized by an N‐Heterocyclic Carbene: Synthesis, Reactivity, and Hydrosilylation Catalysis
Author(s) -
Rit Arnab,
Zanardi Alessandro,
Spaniol Thomas P.,
Maron Laurent,
Okuda Jun
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201408346
Subject(s) - chemistry , carbene , imes , hydrosilylation , medicinal chemistry , cationic polymerization , protonation , zinc , hydride , reactivity (psychology) , dication , catalysis , brønsted–lowry acid–base theory , organic chemistry , photochemistry , molecule , metal , medicine , ion , alternative medicine , pathology
The trinuclear cationic zinc hydride cluster [(IMes) 3 Zn 3 H 4 (THF)](BPh 4 ) 2 ( 1 ) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH 2 ] 2 with a Brønsted acid or by addition of the putative zinc dication [(IMes)Zn(THF)] 2+ . A triply bridged thiophenolato complex 2 was formed upon oxidation of 1 with PhSSPh. Protonolysis of 1 by methanol or water gave the corresponding trinuclear dicationic derivatives. At ambient temperature, 1 catalyzed the hydrosilylation of aldehydes, ketones, and nitriles. Carbon dioxide was also hydrosilylated under forcing conditions when using (EtO) 3 SiH, giving silylformate as the main product.