Mercury-Group 13 Metal Covalent Bonds: A Systematic Comparison of Aluminyl, Gallyl and Indyl Metallo-ligands.

Bimetallic compounds containing direct metal-group 13 element bonds have been shown to display unprecedented patterns of cooperative reactivity towards small molecules, which can be influenced by the identity of the group 13 element. In this context, we present here a systematic appraisal of group 13 metallo-ligands of the type [(NON)E] (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) for E=Al, Ga and In, through a comparison of structural and spectroscopic parameters associated with the trans L or X ligands in linear d complexes of the types LM{E(NON)} and XM'{E(NON)}. These studies are facilitated by convenient syntheses (from the In(I) precursor, InCp) of the potassium indyl species [{K(NON)In}⋅KCp] (1) and [(18-crown-6)KCp] [(NON)In] (1'), and lead to the first structural characterisation of Ag-In and Hg-E (E=Al, In) covalent bonds. The resulting structural, spectroscopic and quantum chemical probes of Ag/Hg complexes are consistent with markedly stronger σ-donor capabilities of the aluminyl ligand, [(NON)Al], over its gallium and indium counterparts.