Arsine and carbene gold(I) complexes with architectures closely related to those of 2-(di-tert-butylphosphino)biphenyl gold(I) complexes have been prepared and structurally characterized. As predicted, 2-(di-tert-butylarsine)biphenyl gold(I) complexes are more electrophilic catalysts in comparison to their phosphine analogues, whereas those based on 4-arylindazole behave similarly to NHC-gold(I) catalysts.