A synthesis and purification route has been developed for base-free trialkylgallium compounds which avoids the use of traditional ether solvents. The R3Ga compound (R = Et, Pr-i) is synthesised in triethylamine, NEt3, which leads to the adducts R3Ga(NEt3). The NEt3 ligand can be readily displaced by the addition of low volatility bidentate, tetradentate or hexadentate tertiary amines to give adducts of the type (R3Ga)(x)L (x = 2, 4, 6), from which base-free R3Ga compounds are obtained by mild thermal dissociation. The synthesis and characterisation of these adducts are described and crystal structures reported for the adducts between R3Ga (R = Et, Pr-i) and the multidentate macrocyclic amines 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane. These are the first reported structural studies of the Et3Ga and (Pr3Ga)-Ga-i molecules in the solid state.A synthesis and purification route has been developed for base-free trialkylgallium compounds which avoids the use of traditional ether solvents. The R3Ga compound (R = Et, Pr-i) is synthesised in triethylamine, NEt3, which leads to the adducts R3Ga(NEt3). The NEt3 ligand can be readily displaced by the addition of low volatility bidentate, tetradentate or hexadentate tertiary amines to give adducts of the type (R3Ga)(x)L (x = 2, 4, 6), from which base-free R3Ga compounds are obtained by mild thermal dissociation. The synthesis and characterisation of these adducts are described and crystal structures reported for the adducts between R3Ga (R = Et, Pr-i) and the multidentate macrocyclic amines 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane. These are the first reported structural studies of the Et3Ga and (Pr3Ga)-Ga-i molecules in the solid state.