Treatment of [Au(C6F5)(SC4H8)] (1) (SC4H8 = tetrahydrothiophene or tht) with HCNC(CH3)C(H)S, CH3SCNC(CH3)C(H)S, (I) or piperidine yields the neutral mononuclear imine complexes [Au(C6F5){NC(H)SC(H)CCH3}] (2) and [Au(C6F5){NC(SCH3)SC(H)CCH3}] (3), or the amine complex [Au(C6F5){N(H)CH2(CH2)3CH2}] (4). The reaction of 1 with SCN(H)C(CH3)C(H)S, (II) affords the thione complex [Au(C6F5){SCN(H)C(CH3)C(H)S}] (5), which, in CH2Cl2via spontaneous intermolecular deprotonation of the thione ligand, self-assembles to an unique tetramer of Au(I), [Au{SCNC(CH3)C(H)S}]4 (6) containing a folded rectangle of Au-atoms with aurophlilic interactions [av. Au⋯Au distance, 3.02(4) Å and av. Au–Au–Au angle, 87(2)°]. N-coordination of the imine complexes has been confirmed by 15N NMR and the crystal structure determination of 2 which exhibits the expected linear N-coordination and intermolecular Au⋯Au [3.345(1) Å] contacts. The crystal structure of 5 shows thione S-coordination of II to the central Au atom.