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

Autor: Trose M; EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST, UK. as411@st-andrews.ac.uk., Burnett S, Bonyhady SJ, Jones C, Cordes DB, Slawin AMZ, Stasch A
Jazyk: angličtina
Zdroj: Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2018 Jul 31; Vol. 47 (30), pp. 10281-10287.
DOI: 10.1039/c8dt01798k
Abstrakt: 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.
Databáze: MEDLINE