Lewis Superacidic Divalent Bis( m ‐terphenyl)element Cations [(2,6‐Mes 2 C 6 H 3 ) 2 E] + of Group 13 Revisited and Extended (E=B, Al, Ga, In, Tl)

Duvinage, Daniel; Malaspina, Lorraine A.; Grabowsky, Simon; Mebs, Stefan; Beckmann, Jens (2022). Lewis Superacidic Divalent Bis( m ‐terphenyl)element Cations [(2,6‐Mes 2 C 6 H 3 ) 2 E] + of Group 13 Revisited and Extended (E=B, Al, Ga, In, Tl). European journal of inorganic chemistry, 26(1) Wiley-VCH 10.1002/ejic.202200482

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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 1–5 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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