Homobimetallic Au(I)–Au(I) and Heterotrimetallic Au(I)–Fe(II)–Au(I) Complexes with Dialkyldithiophosphates and Phosphine Ligands: Structural Characterization, DFT Analysis, and Tyrosinase Inhibitory and Biological Effects

[Image: see text] The role of bridging and terminal ligand electronic and steric properties on the structure and antiproliferative activity of two-coordinated gold(I) complexes was investigated on seven novel binuclear and trinuclear gold(I) complexes synthesized by the reaction of either Au(2)(dppm)Cl(2), Au(2)(dppe)Cl(2), or Au(2)(dppf)Cl(2) with potassium diisopropyldithiophosphate, K[(S-O(i)Pr)(2)], potassium dicyclohexyldithiophosphate, K[(S-OCy)(2)], or sodium bis(methimazolyl)borate, Na(S-Mt)(2), which afforded air-stable gold(I) complexes. In 1–7, the gold(I) centers adopt a two-coordinated linear geometry and are structurally similar. However, their structural features and antiproliferative properties highly depend upon subtle ligand substituent changes. All complexes were validated by (1)H, (13)C{(1)H}, (31)P NMR, and IR spectroscopy. The solid-state structures of 1, 2, 3, 6, and 7 were confirmed using single-crystal X-ray diffraction. A density functional theory geometry optimization calculation was used to extract further structural and electronic information. To investigate the possible cytotoxicities of 2, 3, and 7, in vitro cellular tests were carried out on the human cancerous breast cell line MCF-7. 2 and 7 show promising cytotoxicity.