Isoelectronic Aluminium Analogues of Carbonyl and Dioxirane Moieties

Abstract

We report the anion [Al(NON Ar )(Se)] À (NON Ar = [O(SiMe 2 NAr) 2 ] 2À ,A r = 2,6-iPr 2 C 6 H 3 ), whichi sa ni soelectronic Group 13 metal analogue of the carbonyl group containing an aluminium-selenium multiple bond. It was synthesized in as ingle step from the reaction of the aluminyl anion [Al(NON Ar )] À with elemental selenium. Spectroscopic, crystallographic,and computational analysis confirmed multiple bonding between aluminium and selenium. Addition of as econd equivalent of selenium afforded the diselenirane, [Al(NON Ar )(k 2 -Se 2 )] À ,w hichi sa ni soelectronic analogue of the dioxirane group.

Recent advances in low oxidation state aluminium chemistry

“…The terminal Al-O bonds (1.6362(14)Å) were shorter than those of the related aluminium monoalumoxane species, 48 Compound 32 has also been used to access isoelectronic 'heavy' analogues of carbonyl functionalities. 50 Reaction with one equivalent of selenium and catalytic amounts of tri-nbutylphosphine, as a selenium transfer agent, yielded the aluminium selenide (40, Fig. 13).…”

Carbon Monoxide Activation by a Molecular Aluminium Imide: C−O Bond Cleavage and C−C Bond Formation

“…This strategy has previously been employed by Power, Roesky, and co‐workers (e.g., for IV and V , Figure ), and a related approach has been reported by Coles and co‐workers for the synthesis of an indium imide complex ( VI ) . Similar chemistry has also been employed both by ourselves and by Anker and Coles for the synthesis of molecular aluminium oxide species via the reaction of anionic Al I precursors with N 2 O ( I and II ) …”

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

“…We have mitigated the influence of potassium contacts in aluminum–selenium and indium–nitrogen multiple bonds through cation sequestration. A similar attempt was made in this study by allowing the slow diffusion of a solution of [2.2.2]cryptand into a solution 2 at −30 °C, affording large colorless crystals 3 .…”