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

Abstract

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.

Ruthenium(II)–Arene Metallacycles: Crystal Structures, Interaction with DNA, and Cytotoxicity

“…The structures were solved by direct methods and refined by full-matrix least-squares methods with SHELX. [32] All non-hydrogen atoms were refined anisotropically and the hydrogen atoms of the organic molecules were placed in calculated positions, assigned isotropic thermal parameters, and allowed to ride their parent atoms. The following computer programs and hardware were used: structure solution, SHELXS-2014/7; structure refinement, SHELXL-2014/7.…”

Metalation of 2‐Quinolyl‐Linked (Boranophosphinoyl)methane −Alkali Metal, Alkaline Earth Metal, and Ytterbium(II) Complexes of Monoanionic [CH(iPr2P−BH3)(C9H6N‐2)]− Ligand

“…[23] Recently, we have reported on a series of transition metal complexes supported by a 2-quinolyl-linked (thiophosphinoyl)methanide ligand. [26][27][28] The 2-quinolyl group can provide an additional donor site, resulting in formation of metal methanide complexes with diversified structures. Being inspired by the results of our recent studies, we have also developed a 2-quinolyl-linked (boranophosphinoyl)methanide ligand and investigated its coordination chemistry.…”

Unusual Application for Phosphonium Salts and Phosphoranes: Synthesis of Chalcogenides

“…Thiophosphoranes are versatile compounds and can be used, for example, as ligands in coordination chemistry and in the synthesis of alkynes . Selenophosphoranes were described to be inert in Wittig-type reactions with carbonyl compounds .…”