Abstract:Hydroalumination of H 10 C 5 N-N=C(Ad) with HAliBu 2 yielded the hydrazide H 10 C 5 N-N(AliBu 2 )Ad (4; Ad = adamantyl, NC 5 H 10 = piperidinyl). Compound 4 is monomeric and contains a highly strained AlN 2 heterocycle formed by a donor-acceptor interaction between the Al atom and the -N atom of the hydrazine. Two equivalents of the hydride afforded an adduct with an HAliBu 2 molecule coordinated to 4 by an Al-N and a 3c-2e Al-H-Al bond (5). tBuN=C=O did not insert into the relatively weak Al←N donor-acceptor bond of 4; instead, insertion
The active Lewis pairs (ALPs) 2,6-Me2H8C5N–C(H) = C(SiMe3)–AlR2 (1a: R = tBu, 1b, R = iBu) have strained AlC2N heterocycles and relatively weak Al–N bonds. They react readily with a series of organic azides R′N3 [R′ = Ph, CH2C6H4(4-tBu), tBu, SiMe3, CH2Ph] by cleavage of the heterocycles and addition of the azides with their α-N atoms to the Al atom. The Al–N interactions result in an activation of the azide groups which insert into the C–Si bonds of the vinyl groups with their terminal γ-N atoms. Compounds with approximately planar five-membered AlCN3 heterocycles and intact N3 groups are formed in highly selective reactions.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.