Synthesis and characterization of mono and heteropolynuclear luminescent alkynyl platinum diphenylphosphinous acid/phosphinite complexes

Resumen

The novel anionic mononuclear cis-bis(alkynyl) platinum complexes with a chelated diphenylphosphinous acid/diphenylphosphinite (NBu4)[cis-Pt(C≡6;CR)2{(PPh2O) 2H}] (R=But 1a, Ph 1b) have been prepared by treatment of [cis-Pt(C≡6;CR)2COD] with PPh2(O)H and (NBu4)(acac) in a 1:2:1 molar ratio. The molecular structure of 1a has been determined by single-crystal X-ray diffraction. Neutralization reactions of complexes 1 with 1 equiv. of AgClO4 or CuTfO (TfO=triflate) produce tetranuclear dimetallic complexes [cis-Pt{(PPh2O)2H}(μ-κC α:η2-C≡CR)2M]2 (M=Ag, 2a, 2b; M=Cu 3a, 3b), in which each anionic fragment {Pt}(C≡CR)2- ({Pt}=Pt{(PPh2O)2H}) acts as a μ-η2:η2 bridging ligand towards two different silver(I) or copper(I) centres. Finally, the reactions of (NBu4){Pt}(C≡CR)2 1 with [CuCl]n produce heterodinuclear platinum(II)-copper(I) complexes (NBu4)[cis-Pt{(PPh2O)2H}(μ-κC α:η2-C≡CR)2CuCl] (4a, 4b), in which both alkyne units are η2-coordinated side-on to the copper(I) chloride. All complexes are emissive in frozen CH2Cl2 solutions. © 2002 Elsevier Science B.V. All rights reserved.