Dinuclear metal complexes of a new hybrid phosphine-phosphonodithioate ligand

Reaction of Ph2PCH2OH and {RP(S)(mu-S)}(2) (R = P-C6H4OMe, Lawesson's reagent), in toluene, gave the new hybrid P-III/P-V ligand Ph2PCH2OP(S)(R)SH 1 in high yield. Unfortunately, attempts to crystallise 1 gave, instead, suitable X-ray quality crystals of the Zwitterion Ph2P+(CH2OH)CH2OP(S)(R)S - 1', presumably arising from the presence of some residual formaldehyde. Three homodinuclear complexes [Ru-2(eta(6)-p-(CH3C6H4Pr)-P-i)(2) {mu-Ph2PCH2OP(S)(R)S}Cl-3] (2) and [M-2(mu(5)-C-5(CH3)(5))(2){mu-Ph2PCH2OP(S)(R)S)Cl-3] [M = Rh, 3; M = Ir, 4 (R = p-C6H4OCH3)] were obtained upon reaction of a 1:1 molar ratio of 1 and either [(eta(6)-p-(CH3C6H4Pr)-Pr-i)RuCl(mu-Cl)](2) or [M(mu-Cl)(Cl)(eta(5)-C-5(CH3)(5))(2)](2) (M = Rh and Ir), respectively. The mononuclear Ir-III complex Ir(eta(5)-C-5(CH3)(5))(Rh2PCH2OH)Cl-2 5 was prepared for comparative spectroscopic and crystallographic purposes with 4. All compounds were characterised by a combination of multinuclear NMR and FT-IR spectroscopy and elemental analysis. In addition, the first example of a phosphine-dithiophosphonate ligand 1' along with two homodinuclear complexes 2 center dot CHCl3 and 4 were determined by single crystal X-ray diffraction. Compound 5 displays an intramolecular O(1)-H(1)center dot center dot center dot Cl(2) hydrogen bond to a terminal Ir(III )bound chloride ligand. (C) 2021 Elsevier B.V. All rights reserved.