Two tetramethylcyclopentadienyl gallium(III) compounds Ga(C 5Me 4H) 3 and Cl 2(C 5Me 4H)Ga·pyridine have been prepared and characterized. In contrast, when the syntheses of Ga(C 5Me 4H) 2Cl, Ga(C 5Me 4H)Cl 2 and Me 2Ga(C 5Me 4H) were attempted by metathetical and/or ligand redistribution reactions, the isolated product in each case was a mixture of chemically related compounds rather than single species. When pyridine was added to a solution prepared by combining Ga(C 5Me 4H) 3 and GaCl 3 in a 1:2 mol ratio in diethyl ether, the product was the adduct Cl 2(C 5Me 4H)Ga·pyridine, a yellow–green crystalline solid. An elemental analysis, 1H- and 13C-NMR spectra and an X-ray structural study confirmed the identity of this gallium–nitrogen adduct.