Isolable Pincer-type Dianionic Dialane(6)

Abstract

Although pincer-type main group complexes have attracted considerable attention owing to their unique structures and intriguing reactivity, the isolation of pincer-type dianionic dialane(6) is still elusive. Herein we report the first synthesis of the dianionic dialane(6) species 4 bearing novel redox-active trinitrogen pincer ligands by reduction of the aluminum diiodide precursor 3 with excess potassium graphite. The structure of 4 has been investigated by spectroscopic analysis, X-ray crystallography, and density functional theory calculations, which reveal that 4 possesses an Al–Al single covalent bond and twisted trianionic pincer ligands.

Ligand-enforced geometric constraints and associated reactivity in p-block compounds

“…5b) featuring heavily distorted aluminum centres could be accessed by Su and Wang during these studies. 70 In contrast to the ethane-like structure of reported dianionic dialanes, the hemispheric constraint of the NNN ligand results the formation of an AlN 3 semi-pyramid at each end of the Al-Al bond. The anion also exhibits more exposed metal centres, with potential consequences for coordination chemistry that remain to be explored.…”

Ligand-Enforced Geometries and Associated Reactivity in P-Block Compounds

“…License: CC BY-NC-ND 4.0 during these studies. 60 In contrast to the ethane-like structure of reported dianionic dialanes, the hemispheric constraint of the NNN ligand results the formation of an AlN3 semi-pyramid at each end of the Al-Al bond. The anion also exhibits more exposed metal centres, with potential consequences for coordination chemistry that remain to be explored.…”

Ligand-Enforced Geometries and Associated Reactivity in P-Block Compounds

“…59 Notably, a dianionic dialane (13, Figure 5b) featuring heavily distorted aluminum centres could be accessed by Su and Wang during these studies. 60 In contrast to the ethane-like structure of reported dianionic dialanes, the hemispheric constraint of the NNN ligand results the formation of an AlN3 semi-pyramid at each end of the Al-Al bond. The anion also exhibits more exposed metal centres, with potential consequences for coordination chemistry that remain to be explored.…”