Copper-Catalyzed Huisgen [3 + 2] Cycloaddition of Gold(I) Alkynyls with Benzyl Azide. Syntheses, Structures, and Optical Properties

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• 作者：David V. Partyka ; Lei Gao ; Thomas S. Teets ; James B. Updegraff ; III ; Nihal Deligonul ; Thomas G. Gray
• 刊名：Organometallics
• 出版年：2009
• 出版时间：November 9, 2009
• 年：2009
• 卷：28
• 期：21
• 页码：6171-6182
• 全文大小：1004K
• 年卷期：v.28,no.21(November 9, 2009)
• ISSN：1520-6041

文摘

The copper(I)-catalyzed Huisgen [3 + 2] cycloaddition is a general reaction encompassing wide ranges of organoazide and primarily terminal alkyne reacting partners. Strained internal alkynes can also undergo cycloaddition with azides. We report here that tetrakis(acetonitrile)copper(I) hexafluorophosphate catalyzes the [3 + 2] cycloaddition of (phosphine)- and (N-heterocyclic carbene)gold(I) alkynyls with benzyl azide. Isolated yields of up to 96% result. The reaction protocol broadly tolerates functionalities on the alkynyl reagent. Gold(I) triazolate products form with complete 1,4-regioselectivity. Some 15 new gold(I) triazolates are reported along with crystal structures of nine. Triazolate complexes bearing polycyclic aromatic substituents show dual singlet- and triplet-state luminescence from excited states localized on the aromatic fragment. Time-resolved emission experiments find long lifetimes consistent with triplet emission parentage. Absorption and emission transitions are analyzed with time-dependent density-functional theory calculations.