Fullerene C60 reacts with dimagnesium(i) compounds LMgMgL, where L is a monoanionic β-diketiminate ligand, to contact ion complexes [(LMg)nC60], where n is predominantly 2, 4 or 6.

The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L = HC(PhP[double bond, length as m-dash]NDip), Dip = 2,6-PrCH; M = Li, Na, K) with "GaI", InBr or TlBr afforded the monomeric group 13 metal(i) complexes LE:, E = Ga (1), In (2) and Tl (3) in moderate yields, and small quantities of LGaI4 in the case of Ga, respectively. The molecular structures of LE: 1-3 from X-ray single crystal diffraction show them to contain puckered six-membered rings with N,N'-chelating methanide ligands and two-coordinated metal(i) centres. Reduction reactions of LAlI5, prepared by iodination of LAlMe, were not successful and no aluminium(i) congener could be prepared so far. DFT studies on LE:, E = Al-Tl, were carried out and support the formulation as an anionic, N,N'-chelating methanide ligand coordinating to group 13 metal(i) cations. The HOMOs of the molecules for E = Al-In show a dominant contribution from a metal-based lone pair that is high in s-character.

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