Synthesis, characterization, and optical properties of pentafluorophenyl complexes with a Pt-Cd bond

Article abstract of DOI:10.1021/om049719w

Novel bimetallic neutral [(C₆F₅) ₄PtCd(cyclen)] and [(C₆F₅) ₂(C≡CPh)₂PtCd(cyclen)] (1, 2) and cationic [(C ₆F₅)₂(bzq)PtCd(cyclen)](ClO₄) (3) pentafluorophenylplatinum(II)-cadmium-(II) derivatives have been prepared by treatment of the adequate anionic starting precursors [Pt(C₆F ₅)₂X₂]^n- (n = 2, X = C ₆F₅, C≡CPh; n = 1, X₂ = bzq) with Cd(ClO₄)₂ and cyclen. X-ray diffraction studies on complexes 1, 2, and 3 show that they are stabilized by a short Pt→Cd donor acceptor bond and, additionally, in complex 2 the Cd center is also coordinated to the C_α of one of the two alkynyl groups. In contrast, treatment of the binuclear compound [NBu₄]₂-[Pt ₂(μ-Cl)₂(C₆F₅)₄] with [Cd(cyclen)(MeOH)₂](ClO₄)₂ afforded the tetranuclear derivative [Pt(C₆F₅)₂Cl(μ-Cl) Cd(cyclen)]₂ (4) (X-ray), in which Pt and Cd atoms are connected by a μ₃-Cl bridging ligand, and the binuclear cadmium complex [Cd ₂(μ-Cl)₂(cyclen)₂](ClO₄) ₂ (5) (X-ray), in which two "Cd(cyclen)" fragments are bridged by two chlorine atoms. The photoluminescent properties of complexes 1-3 have also been examined and compared with those of their corresponding anionic parent compounds [NBu₄]₂[Pt(C₆F ₅)₄], [PMePh₃]₂[Pt(C ₆F₅)₂(C≡CPh)₂], and [NBu ₄][Pt(C₆F₅)₂(bzq)] (6).