Zwitterionic and Donor-Stabilized N-Heterocyclic Silylenes (NHSis) for Metal-Free Activation of Small Molecules

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• 作者：Shenglai Yao ; Yun Xiong ; Matthias Driess
• 刊名：Organometallics
• 出版年：2011
• 出版时间：April 11, 2011
• 年：2011
• 卷：30
• 期：7
• 页码：1748-1767
• 全文大小：1854K
• 年卷期：v.30,no.7(April 11, 2011)
• ISSN：1520-6041

文摘

This account describes recent progress (>2006) in the synthesis and structural characterization of isolable N-heterocyclic silylenes (NHSi's) and their fascinating reactivities with respect to an emergent topic in main-group chemistry: metal-free small-molecule activation. Since the seminal discovery of stable N-heterocyclic silicon analogues of nucleophilic Wanzlick鈭扐rduengo-type carbenes in 1994, new types of NHSi's have emerged with unique electronic features and strikingly different reactivities. Among them, the first zwitterionic (ylide-like) silylene LSi: (L = CH[(C鈺怌H₂)CMe][NAr]₂; Ar = 2,6-Prⁱ₂C₆H₃) and unprecedented N-heterocyclic bis(silylenes) with amidinate ligands and Si(I)鈭扴i(I) bonds were synthesized. Their striking electronic structures open new doorways to metal-free activation of C鈭扝, C鈭扻, Si鈭扻, E鈭扝 (E = group 15, group 16 elements), P鈭扨, E鈭扥 (E = C, N), and E鈭扙 bonds (E = O, S, Se, Te).