Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium

Dalton Transactions : an International Journal of Inorganic Chemistry
Michael TroseAndreas Stasch

Abstract

The mixed N-heterocyclic carbene (NHC) complexes NHCAlHxI3-x, where NHC is IDip or IMes ((HCNAr)2C:, Ar = 2,6-iPr2C6H3 = Dip (IDip); or 2,4,6-Me3C6H2 = Mes (IMes)), x = 1 or 2, were either prepared from NHCAlH3 and NHCAlI3 or by halogenation of NHCAlH3 with MeI. Reaction of [(IDip)AlHxI3-x], with x = 0-3, with another equivalent of IDip afforded either fluxional equilibria in benzene solution for x = 0, no reaction for x = 3, or the new mixed normal-abnormal NHC-coordinated ionic complexes [(IDip)AlH2(aIDip)]I (9) and [(IDip)AlHI(aIDip)]I (10), where aIDip is the abnormal IDip carbene tautomer bonded through its 4-position. The molecular structures of 9 and 10 were determined and show slightly shorter Al-C(aIDip) than Al-C(IDip) distances. In addition, a complex containing [(IDip)AlI2(aIDip)]I (11) was structurally characterized though could not intentionally be synthesised. Possible formation mechanisms for 9-11 are discussed and the normal and abnormal IDip coordination to the aluminium(iii) centre is believed to occur for steric reasons.

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Citations

Aug 17, 2018·Chemistry : a European Journal·Daniel Franz, Shigeyoshi Inoue
Aug 4, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Andreas HockUdo Radius
Aug 28, 2021·Chemical Reviews·Matthew M D RoyEric Rivard

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