Paramagnetic diazabutadienegallium(II or III) complexes, [(Ar-DAB)2Ga] and [{(Ar-DAB.)GaX}2] (X=Br or I; Ar-DAB={N(Ar)C(H)}2, Ar=2,6-diisopropylphenyl), have been prepared by reactions of an anionic gallium N-heterocyclic carbene analogue, [K(tmeda)][:Ga(Ar-DAB)], with either “GaI” or [MoBr2(CO)2(PPh3)2]. A related InIII complex, [(Ar-DAB.)InCl2(thf)], has also been prepared. These compounds were characterised by X-ray crystallography and EPR/ENDOR spectroscopy. The EPR spectra of all metal(III) complexes incorporating the Ar-DAB ligand, [(Ar-DAB.)MX2(thf)n] (M=Al, Ga or In; X=Cl or I; n=0 or 1) and [(Ar-DAB)2Ga], confirmed that the unpaired spin density is primarily ligand centred, with weak hyperfine couplings to Al (a=2.85 G), Ga (a=17—25 G) or In (a=26.1 G) nuclei. Changing the N substituents of the diazabutadiene ligand to tert-butyl groups in the gallium complex, [(tBu-DAB.)GaI2] (tBu-DAB={N(tBu)C(H)}2), changes the unpaired electron spin distribution producing 1H and 14N couplings of 1.4 G and 8.62 G, while the aryl-substituted complex, [(Ar-DAB.)GaI2], produces couplings of about 5.0 G. These variations were also manifested in the gallium couplings, namely aGa ∼1.4 G for [(tBu-DAB.)GaI2] and aGa ∼25 G for [(Ar-DAB.)GaI2]. The EPR spectra of the gallium(II) and indium(II) diradical complexes, [{(Ar-DAB.)GaBr}2], [{(Ar-DAB.)GaI}2], [{(tBu-DAB.)GaI}2] and [{(Ar-DAB.)InCl}2], revealed doublet ground states, indicating that the GaGa and InIn bonds prevent dipole–dipole coupling of the two unpaired electrons. The EPR spectrum of the previously reported complex, [(Ar-BIAN.)GaI2] (Ar-BIAN=bis(2,6-diisopropylphenylimino)acenaphthene) is also described. The hyperfine tensors for the imine protons, and the aryl and tert-butyl protons were obtained by ENDOR spectroscopy. In [(Ar-DAB.)GaI2], gallium hyperfine and quadrupolar couplings were detected for the first time.