Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium
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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 a 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.
Trose , M , Burnett , S , Bonyhady , S J , Jones , C , Cordes , D B , Slawin , A M Z & Stasch , A 2018 , ' Normal and abnormal NHC coordination in cationic hydride iodide complexes of aluminium ' Dalton Transactions , vol. In press . https://doi.org/10.1039/C8DT01798K
© 2018 The Author(s). This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1039/C8DT01798K
DescriptionWe thank the University of St Andrews and the EPSRC UK National Mass Spectrometry Facility (NMSF) at Swansea University.
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