Ring expansion of alumoles with organic azides: selective formation of six-membered aluminum–nitrogen heterocycles

Abstract

A cyclopentadienyl-substituted alumole is shown to undergo ring expansions with a series of organic azides, affording 1,2-azaaluminabenzenes either with or without an azo group.

Exploring Cu/Al cluster growth and reactivity: from embryonic building blocks to intermetalloid, open-shell superatoms

“…Notably, alkynes are known to react with organometallic Al compounds to yield cycloaddition products. 44 …”

“…Notably, alkynes are known to react with organometallic Al compounds to yield cycloaddition products. 44 When a toluene solution of 1 is treated with an excess of 3hexyne (20 C), a color change from deep-green to orange-brown is observed within a few minutes. The cluster degradation reaction from 1 to 2 is accompanied by consumption of four equivalents 3-hexyne per molecule of 1 as identied by in situ 1 H-NMR spectroscopy (see ESI, Fig.…”

The Field of Main Group Lewis Acids and Lewis Superacids: Important Basics and Recent Developments

“…[146] More recently, alumoles with t Bu and Cp''' substituents on Al atom were reported. [147] Like the Br-substituted analog, [145] t Bu derivative exists as a dimer in the solid state (Al … Al distance of 2.638(1) Å), in solution the dimer-monomer equilibrium was observed, with the dimeric form observed at À 50 °C and monomeric form is dominant at room temperature and above. No complex with THF was formed at room temperature.…”

“…Alumoles: These five-membered cyclic Al-containing LA were extensively studied experimentally (Scheme 27). [144][145][146][147][148] Use of the bulky protecting group Mes* (2,4,6-( t Bu) 3 C 6 H 2 ) allowed to synthesize monomeric "alumole" Mes*AlC 4 Et 4 [144] which is stable under inert atmosphere, but easily hydrolyzes on air. It does not react with such LB as Et 2 O and THF in deuterobenzene solution due to bulky protective Mes* substituent.…”

Transfer of an Aluminium Atom: An Avenue to Aluminium Heterocycles

“…In a rare case, alumoles derived from Roesky's [HC(CMeNDipp)2]Al (Dipp = 2,6-diisopropylphenyl) 58 have also found applications in aggregation-induced emission (AIE) in the solid state although such fluorescence emissions in benzene are almost negligible. 59 Despite such utility, synthetic routes towards alumoles are exceedingly limited and largely rely on the employment of organo-dilithium [60][61][62][63][64][65][66] or zirconocene-based 56,[67][68][69] reagents. There is only a single report describing alumole syntheses via carboboration of the aluminum dialkynyl LAl(CCR)2 (L = N, N-chelate ligand and R = organic group) with B(C6F5)3 by Roesky, Zhu, Wang et al 59…”