Isoelectronic Aluminium Analogues of Carbonyl and Dioxirane Moieties

Abstract

We report the anion [Al(NONAr)(Se)]− (NONAr=[O(SiMe2NAr)2]2−, Ar=2,6‐iPr2C6H3), which is an isoelectronic Group 13 metal analogue of the carbonyl group containing an aluminium–selenium multiple bond. It was synthesized in a single step from the reaction of the aluminyl anion [Al(NONAr)]− with elemental selenium. Spectroscopic, crystallographic, and computational analysis confirmed multiple bonding between aluminium and selenium. Addition of a second equivalent of selenium afforded the diselenirane, [Al(NONAr)(κ2‐Se2)]−, which is an isoelectronic analogue of the dioxirane group.

An Aluminum Telluride with a Terminal Al=Te Bond and its Conversion to an Aluminum Tellurocarbonate by CO2 Reduction

“…The solid‐state structure of 3‐Se (Figure 2, Bottom) exhibits a geometry similar to 3‐Te (Middle) featuring an Al 2 (μ‐Se) 2 core with the NHC and Tipp substituents bound to Al centers oriented in a trans fashion. Al1−Se1 bond length (2.386(1), 2.402(2) Å) is within the range of the typical Al−Se single bond length (2.34–2.54 Å) of reported aluminum selenides, [1b, 2a, 7a,b,d, 8e, 9a, 15] but notably longer than the Al=Se double bond length (2.2032(6) Å) of Va [12e] . 77 Se NMR of the IMe 4 ‐substituted 3‐Se exhibits a chemical shift at −460.5 ppm, which is in a higher field than that of the I i Pr‐substituted 2‐Se (−355.7 ppm).…”

“…With the development of anionic aluminyl chemistry, wherein additional stabilization is achieved through interaction with alkali metals, this strategy has been employed for the isolation of discrete Al=Ch bonds [12] . For example, Coles and co‐workers isolated [Al=Se] − ( Va ) [12e, 13] and [Al=Te] − ( Vb ) [12c] . With increased anionic character and nucleophilicity, both species showed remarkably nucleophilic reactivity towards Se and CO 2 [12c, 13] …”

An Aluminum Telluride with a Terminal Al=Te Bond and its Conversion to an Aluminum Tellurocarbonate by CO2 Reduction

“…The solid‐state structure of 3‐Se (Figure 2, Bottom) exhibits a geometry similar to 3‐Te (Middle) featuring an Al 2 (μ‐Se) 2 core with the NHC and Tipp substituents bound to Al centers oriented in a trans fashion. Al1−Se1 bond length (2.386(1), 2.402(2) Å) is within the range of the typical Al−Se single bond length (2.34–2.54 Å) of reported aluminum selenides, [1b, 2a, 7a,b,d, 8e, 9a, 15] but notably longer than the Al=Se double bond length (2.2032(6) Å) of Va [12e] . 77 Se NMR of the IMe 4 ‐substituted 3‐Se exhibits a chemical shift at −460.5 ppm, which is in a higher field than that of the I i Pr‐substituted 2‐Se (−355.7 ppm).…”