Abstract
The behavior of the potassium alumanyl, [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3), toward organic nitriles has been investigated. In common with earlier studies of the reactivity of charge neutral Al(I) species with multiply bonded small molecules, it is suggested that the initial step in all the reactions involves [2 + 1] cycloaddition and the generation of an [η2-C=N-Al] alumina azacyclopropane unit. In the cases of o- and m-tolyl-substituted aryl nitriles, this species is too kinetically labile to allow its isolation and undergoes C-C coupling via immediate Al-C/C≡N insertion to yield the alumina diazabutadiene derivatives. In contrast, the increased steric profile of alkyl nitriles imposes a marked influence on the nature of the products formed. Consistent with the proposed sequential pathway, reaction of [{SiNDipp}AlK]2 with t-BuCN provides an isolable alumina cyclopropane species that is kinetically resistant to onward reaction with a further nitrile equivalent. While reduction in the alkyl nitrile steric demands by use of i-PrCN again facilitates C-C bond formation, the crowding of the Al center by the resultant alumina-diazabutadienediide moiety appears to be beyond the limit of kinetic viability, resulting in an unusual 2-fold C-H to N-H isomerization from one of the C-iso-propyl substituents and the isolation of a 1-alumina-2,5-diazabutadiene structure.