Metallacyclic complexes. Synthesis of metallathietane-3,3-dioxide (metallacyclosulphone) complexes of platinum(II), palladium(II), and nickel(II); crystal structure of trans-2,4-diphenyl-1, 1-bis(triphenylarsine)platinathietane-3,3-dioxide

Abstract

The reactions of the complexes [MCl₂L₂] with the dianion [PhCHS(O)₂CHPh]^2– afford, in high yield, the metallathietane-3,3-dioxide complexes [[graphic omitted]HPh}L₂](M = Pt, L = AsPh₃,PPh₃, or SEt₂; M = Pd, L = PPh₃, PMe₃, or PEt₃; M = Ni, L = PMe₃, L₂= Ph₂PCH₂CH₂PPh₂). Treatment of [P[graphic omitted]HPh}(SEt₂)₂] with carbon monoxide, 2,2′-bipyridyl (bipy), or cyclo-octa-1,5-diene (cod) results in displacement of one diethyl sulphide ligand per platinum to afford the complexes [P[graphic omitted]HPh)}(CO)(SEt₂)], [{P[graphic omitted]HPh](SEt₂)}₂,(µ-bipy)], and [{P[graphic omitted]HPh](SEt₂)}₂(µ-cod)] respectively. A single-crystal X-ray diffraction study has been carried out on [P[graphic omitted]HPh}(AsPh₃)₂]·CH₂Cl₂.2H₂O(1a). The crystals are orthorhombic, space group Pbca, Z= 8, in a unit cell with a= 18.29(2), b= 24.65(2), and c= 22.07(5)Å. The structure has been refined to R 0.0725 (R′ 0.0725) for 3 734 independent reflections withI 2.5σ(I). The platinathietane-3,3-dioxide ring is slightly puckered (fold angle = 24.5°) with no substantial Pt ⋯ S transannular interaction.