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 Rh-I, Ir-I and Au-I metal complexes derived from 2-quinolyl-linked (thiophosphoranyl)methane CH2(iPr(2)P=S)(C9H6N-2) (A) are reported. Metathesis reactions of 2-quinolyl-thiophosphinoyl potassium complex [K{CH(iPr(2)P-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(iPr(2)P=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(iPr(2)P=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(iPr(2)P-S)(C9H6N-2)}] (6), featuring an aurophilic interaction. Meanwhile, the metathesis reaction of 1 with 1 equiv. of gold(I) complex [AuCl((NHC)-N-IPr)] {(NHC)-N-IPr = C[N(2,6-iPr(2)C(6)H(3))CH](2)} afforded a monomeric two-coordinate monoaurated product, 2-quinolyl-thiophosphinoyl-gold(I) N-heterocyclic carbene complex [Au((NHC)-N-IPr){CH(iPr(2)P-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.