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

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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 normalabnormal 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.

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

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Publication details

The article was received on 04 May 2018, accepted on 10 Jul 2018 and first published on 11 Jul 2018


Article type: Paper
DOI: 10.1039/C8DT01798K
Citation: Dalton Trans., 2018, Advance Article
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    Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium

    M. Trose, S. Burnett, S. J. Bonyhady, C. Jones, D. B. Cordes, A. M. Z. Slawin and A. Stasch, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT01798K

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