An Unprecedented Phosphinamidic Gold(III) Metallocycle: Synthesis via Tin(IV) Precursors, Structure, and Multicomponent Catalysis

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• 作者：Pascual Oa-Burgos^† ; ; Ignacio Fernndez^† ; ; Laura Roces^‡ ; ; Laura Torre Fernndez^‡ ; ; Santiago Garca-Granda^‡ ; ; Fernando Lpez Or
• 刊名：Organometallics
• 出版年：2009
• 出版时间：March 23, 2009
• 年：2009
• 卷：28
• 期：6
• 页码：1739-1747
• 全文大小：253K
• 年卷期：v.28,no.6(March 23, 2009)
• ISSN：1520-6041

文摘

A straightforward method of synthesizing cycloaurated gold(III) phosphinamide-based molecules starting from their ortho-tin(IV) derivatives in excellent yields is described. The structure of the tin and gold complexes has been investigated by multinuclear magnetic resonance (¹H, ¹³C, ¹⁵N,³¹P, ¹¹⁹Sn) and single-crystal X-ray diffraction. In solution and in the solid state the ortho-functionalized phosphinamide moiety acts as a new C−C−P−O pincer ligand with formation of asymmetric five-membered ring metallocycles. Intramolecular PO coordination to tin(IV) leads to a distorted trigonal-bipyramid configuration for the metal, while in the gold(III) metallocyclic complex the metal shows a square-planar geometry. The new Au(III) complex has been applied in multicomponent (A³) coupling processes, providing a variety of propargylamines in quantitative yields under very mild conditions without the use of any activator or additive. Diffusion NMR studies showed that the catalyst is present as a monomer in acetonitrile solution, while a slight charge-induced aggregation seems to take place in chloroform.