Dinuclear Zinc Hydride Supported by an Anionic Bis(N‐Heterocyclic Carbene) Ligand. Issue 2 (25th November 2013)

• Record Type: Journal Article
• Authors: Rit, Arnab; Spaniol, Thomas P.; Okuda, Jun
• Is Part Of: Chemistry, an Asian journal. Volume 9:Issue 2(2014:Feb.)
• Page Start: 612
• Page End: 619
• Publication Date: 2013-11-25
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201301268
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Methylene‐linked bis(<italic>N</italic>, <italic>N</italic>′‐di‐<italic>tert</italic>‐butylimidazol‐2‐ylidene) <bold>1</bold> reacted with diethylzinc to give dinuclear zinc ethyl compound <bold>2</bold>, which contains a formally anionic bis(carbene) ligand as a result of deprotonation of the methylene bridge. The reaction of <bold>2</bold> with PhSiH₃ gave the phenylsilyl compound <bold>3</bold>. The zinc hydride <bold>4</bold> was obtained by the reaction of <bold>2</bold> with LiAlH₄ or Ph₃SiOH followed by treatment with PhSiH₃. X‐ray diffraction studies show that compounds <bold>2</bold>, <bold>3</bold>, and <bold>4</bold> all have a similar dimeric structure with <italic>D</italic>_{2<italic>h</italic>} symmetry. The reaction of hydride <bold>4</bold> with carbon dioxide and <italic>N</italic>, <italic>N</italic>′‐diisopropylcarbodiimide gave formato (<bold>5</bold>) and formamidinato (<bold>7</bold>) derivatives as a result of the insertion of the heterocumulene into both ZnH bonds. Reaction with Ph₂CO gave the diphenylmethoxy compound <bold>6</bold>. Hydride <bold>4</bold> shows catalytic activity in the hydrosilylation of 1, 1‐diphenylethylene and methanolysis of silanes.</p> </abstract>