Synthesis and Structural Characterization of Mono‐ and Bimetallic Rhodium(I), Iridium(I) and Gold(I) Methanide and Methandiide Complexes from 2‐Quinolyl‐Linked (Thiophosphoranyl)methane

The synthesis and structural characterization of RhI, IrI and AuI metal complexes derived from 2-quinolyl-linked (thiophosphoranyl)methane CH2(iPr2P=S)(C9H6N-2) (A) are reported. Metathesis reactions of 2-quinolyl-thiophosphinoyl potassium complex [K{CH(iPr2P-S)(C9H6N-2)}]n (1) with 1 equiv. of [MCl(COD)]2 (M = Rh, Ir; COD = cycloocta-1,5-diene) afforded monomeric 2-quinolyl-thiophosphinoyl-rhodium(I) and iridium(I) complex [M(COD){CH(iPr2P=S)(C9H6N-2)}] {M = Rh (2), Ir (3)}, respectively. Upon treatment of 1 with 2 equiv. of [MCl(COD)]2 (M = Ir, Rh), bimetallic complexes [M(COD){CH(iPr2P=S)(C9H6N-2)(M(COD)Cl)}] {M = Rh (4), Ir (5)} were obtained. The reaction of 1 with [AuCl(PPh3)] afforded a geminal dinuclear gold(I) methandiide complex [{Au(PPh3)}2{C(iPr2P-S)(C9H6N-2)}] (6), featuring an aurophilic interaction. Meanwhile, the metathesis reaction of 1 with 1 equiv. of gold(I) complex [AuCl(IPrNHC)] {IPrNHC = C[N(2,6-iPr2C6H3)CH]2} afforded a monomeric two-coordinate monoaurated product, 2-quinolyl-thiophosphinoyl-gold(I) N-heterocyclic carbene complex [Au(IPrNHC){CH(iPr2P-S)(C9H6N-2)}] (7). The structures of 3–7 have been determined by X-ray crystallography and the UV/Vis absorption properties of 2–6 have also been studied.