Gold(I) Complexes of the Geminal Phosphinoborane tBu(2)PCH(2)BPh(2)

[Image: see text] In this work, we explored the coordination properties of the geminal phosphinoborane tBu(2)PCH(2)BPh(2) (2) toward different gold(I) precursors. The reaction of 2 with an equimolar amount of the sulfur-based complex (Me(2)S)AuCl resulted in displacement of the SMe(2) ligand and formation of linear phosphine gold(I) chloride 3. Using an excess of ligand 2, bisligated complex 4 was formed and showed dynamic behavior at room temperature. Changing the gold(I) metal precursor to the phosphorus-based complex, (Ph(3)P)AuCl impacted the coordination behavior of ligand 2. Namely, the reaction of ligand 2 with (Ph(3)P)AuCl led to the heterolytic cleavage of the gold–chloride bond, which is favored over PPh(3) ligand displacement. To the best of our knowledge, 2 is the first example of a P/B-ambiphilic ligand capable of cleaving the gold–chloride bond. The coordination chemistry of 2 was further analyzed by density functional theory calculations.