Chemistry of vinylidene complexes. XXV. Synthesis and reactions of binuclear mu-vinylidene RePt complexes containing phosphite ligands. Spectroscopic, structural and electrochemical study

Oleg S. Chudin, Victor V. Verpekin, Alexander A. Kondrasenko, Galina Burmakina, Dmitry A. Piryazev, Alexander D. Vasiliev, Nina Pavlenko, Dmitry Zimonin, Anatoly Rubaylo

Research output: Contribution to journalArticlepeer-review

Abstract

Reactions of Cp(CO)(2)Re=C=CHPh with Pt[P(OR)(3)](4) (R = Pr-i, Et, Ph) gave binuclear mu-vinylidene complexes Cp(CO)(2)RePt(mu-C=CHPWW(OR)(3)](2). Treatment of the previously synthesized Cp(CO)(2)Re(mu-C=CHPh)Pt(PPh3)(2) with triisopropylphosphite or triethylphosphite resulted in a stepwise substitution of PPh3 ligands, leading to the disubstituted Cp(CO)(2)RePt(mu-C=CHPh)[P(OR)(3)](2) and monosubstituted Cp(CO)(2)RePt(mu-C=CHPh)[P(OR)(3)] (PPh3) (R = Pr-i or Et) species, while no triphenylphosphine ligand substitution in the reaction with P(OPh)(3) occurs at all. The monosubstituted Cp(CO)(2)RePt(mu-C=CHPh)IP(OR)(3)](PPh3) (R = Pe(i), Et, Ph) species were also obtained by reacting Cp(CO)(2)Re=C=CHPh with mixed-ligand complexes Pt(PPh3)(3)L (L = P(OPi)(3), P(OEt)(3), P (OPh)(3)). Reactions of Cp(CO)(2)RePt(mu-C=CHPh)LL' = L' = P(OPri)(3), P(OEt)(3), P(OPh)(3); L = P(OPri)(3), P(OEt)(3), P(OPh)(3), L' = PPh3) with Co-2(CO)(9) yield tricarbonyl vinylidene species Cp(CO)(2)RePt(mu-C=CHPh)IP(OR)(3)](CO) (R = Pr-i, Et, Ph). The obtained compounds were characterized by IR and H-1, C-13, P-31 NMR spectroscopy. The molecular structures of Cp(CO)(2)RePt(mu-C=CHPh)[P(OPi)(3)](2), Cp(CO)(2)RePt(mu-C=CHPh)[P(OPri)(3)](PPh3) and Cp(CO)(2)RePt(mu-C=CHPh)[P(OPri)(3)](CO) were determined by X-ray diffraction study. The redox properties of the new complexes and their reactions of chemical oxidation were studied.

Original languageEnglish
Pages (from-to)119463
Number of pages13
JournalInorganica Chimica Acta
Volume505
DOIs
Publication statusPublished - 24 May 2020

Keywords

  • Vinylidene complexes
  • Rhenium
  • Platinum
  • NMR
  • X-ray diffraction
  • Redox properties
  • PLATINUM HYDRIDE COMPLEXES
  • OXIDATIVE DEHYDRODIMERIZATION
  • HETEROMETALLIC COMPLEXES
  • UNSATURATED MOLECULES
  • MANGANESE-PLATINUM
  • CRYSTAL-STRUCTURES
  • BRIDGED COMPLEXES
  • BOND ACTIVATION
  • METAL COMPLEXES
  • REACTIVITY

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