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Lewis Superacidic Divalent Bis(m‐terphenyl)element Cations [(2,6‐Mes2C6H3)2E]+ of Group 13 Revisited and Extended (E=B, Al, Ga, In, Tl)

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The first two-coordinate diarylindinium cation [2,6-Mes2C6H3)2In]+ was prepared and fully characterized.


Abstract

In a combined experimental and computational study, the molecular and electronic structures of the divalent bis(m-terphenyl)element cations [(2,6-Mes2C6H3)2E]+ of group 13 (1, E=B; 2, E=Al; 3, E=Ga; 4, E=In; 5, E=Tl) were investigated. The preparation and characterization of 2, 3 and 5 were previously reported by Wehmschulte's (Organometallics 2004, 23, 1965–1967; J. Am. Chem. Soc. 2003, 125, 1470–1471) and our groups (Organometallics 2009, 28, 6893–6901). The indinium ion 4 was prepared and fully characterized for the first time. Attempts to prepare the borinium ion 1 by fluoride or hydride abstraction were unsuccessful. The electronic structures of 15 and the stabilization by the bulky m-terphenyl substituents were analyzed using quantum chemical calculations and compared to the divalent bis(m-terphenyl)pnictogenium ions [(2,6-Mes2C6H3)2E]+ of group 15 (6, E=P; 7, E=As; 8, E=Sb; 9, E=Bi) previously investigated by our group (Angew. Chem. Int. Ed. 2018, 57, 10080–10084). The calculated fluoride ion affinities (FIA) of 1–9 are higher than that of SbF5, which classifies them as Lewis superacids.

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