A Cationic Zinc Hydride Cluster Stabilized by an N‐Heterocyclic Carbene: Synthesis, Reactivity, and Hydrosilylation Catalysis1. Issue 48 (24th September 2014)

• Record Type: Journal Article
• Authors: Rit, Arnab; Zanardi, Alessandro; Spaniol, Thomas P.; Maron, Laurent; Okuda, Jun
• Is Part Of: Angewandte Chemie international edition. Volume 53:Issue 48(2014)
• Page Start: 13273
• Page End: 13277
• Publication Date: 2014-09-24
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201408346
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The trinuclear cationic zinc hydride cluster [(IMes)₃Zn₃H₄(THF)](BPh₄)₂ (<bold>1</bold>) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH₂]₂ with a Brønsted acid or by addition of the putative zinc dication [(IMes)Zn(THF)]²⁺. A triply bridged thiophenolato complex <bold>2</bold> was formed upon oxidation of <bold>1</bold> with PhSSPh. Protonolysis of <bold>1</bold> by methanol or water gave the corresponding trinuclear dicationic derivatives. At ambient temperature, <bold>1</bold> catalyzed the hydrosilylation of aldehydes, ketones, and nitriles. Carbon dioxide was also hydrosilylated under forcing conditions when using (EtO)₃SiH, giving silylformate as the main product.</p> </abstract>