Synthesis and Characterization of Palladium and Nickel Complexes with Positively Charged Triphosphine Ligands and Their Use as Electrochemical CO2-Reduction Catalysts

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Abstract

The synthesis and characterization of [M(Bu3P+etpE)Br](BF4)2 (where M = Ni or Pd and Bu3P+etpE = [(Bu3PCH2CH2)P(CH2CH2PEt2)2]+) and [M(etpPBu3+)Br]Br(BF4)4 (where M = Ni or Pd and etpPBu3+ = {PhP[CH2CH2P(CH2CH2PBu3)2]2}4+) are described. The structure of [Ni(etpPbu3+)Br]Br(BF4)4 has been determined by X-ray diffraction. Treatment of [Pd-(Bu3P+etpE)Br](BF4)2 with AgBF4 in acetonitrile produced[Pd(Bu3P+etpE)(CH3CN)](BF4)3. The latter compound has also been characterized by single-crystal X-ray diffraction methods. Electrochemical studies indicate that this compound and its closely related methyl analog, [Pd(Me3P+etpE)(CH3CN)](BF4)3, are catalysts for the electrochemical reduction of CO2 to CO in acidic dimethylformamide solutions. Kinetic and mechanistic studies of this catalyticreaction are reported.
Original languageAmerican English
Pages (from-to)5779-5791
Number of pages13
JournalOrganometallics
Volume16
DOIs
StatePublished - 1997

NREL Publication Number

  • NREL/JA-450-23140

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