A Silyliumylidene Cation Stabilized by an Amidinate Ligand and 4‐Dimethylaminopyridine. Issue 35 (12th July 2013)

• Record Type: Journal Article
• Authors: Yeong, Hui‐Xian; Xi, Hong‐Wei; Li, Yongxin; Lim, Kok Hwa; So, Cheuk‐Wai
• Is Part Of: Chemistry. Volume 19:Issue 35(2013)
• Page Start: 11786
• Page End: 11790
• Publication Date: 2013-07-12
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201300255
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [<bold>L</bold>Si:]₂ (<bold>1</bold>; <bold>L</bold>=PhC(N<italic>t</italic>Bu)₂) with one equivalent of <italic>N</italic>‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe₂C₅H₄NSiMe₃]OTf and two equivalents of DMAP in THF afforded [<bold>L</bold>Si(DMAP)]OTf (<bold>2</bold>). The ambiphilic character of <bold>2</bold> is demonstrated from its reactivity. Treatment of <bold>2</bold> with <bold>1</bold> in THF afforded the disilylenylsilylium triflate [<bold>L′</bold>₂(<bold>L</bold>)Si]OTf (<bold>3</bold>; <bold>L′</bold>=<bold>L</bold>Si:) with the displacement of DMAP. The reaction of <bold>2</bold> with [K{HB(<italic>i</italic>Bu)₃}] and elemental sulfur in THF afforded the silylsilylene [<bold>L</bold>SiSi(H){(N<italic>t</italic>Bu)₂C(H)Ph}] (<bold>4</bold>) and the base‐stabilized silanethionium triflate [<bold>L</bold>Si(S)DMAP]OTf (<bold>5</bold>), respectively. Compounds <bold>2</bold>, <bold>3</bold>, and <bold>5</bold> have been characterized by X‐ray crystallography.</p> </abstract>