Synthesis and characterization of water-soluble [Pd(triphosphine)(CH{sub 3}CN)](BF{sub 4}){sub 2} complexes for CO{sub 2} reduction
- National Renewable Energy Lab., Golden, CO (United States)
The syntheses of the triphosphine ligands RP(CH{sub 2}CH{sub 2}PR{sub 2}{prime}){sub 2} (R = CH{sub 2}CH{sub 2}CH{sub 2}OH and R{prime} = Et, HOPetpE; R = Ph and R{prime} = CH{sub 2}CH{sub 2}P(O)(OEt){sub 2}, etpEPO; R = Me{sub 2}N and R {prime} = Et, MNetpE; R = i-Pr{sub 2}N and R{prime} = Et, IPNetpE; R = Ph and R{prime} = NMe{sub 2}, etpMN) are described. The reaction of [Pd(CH{sub 3}CN){sub 4}](BF{sub 4}){sub 2} with these ligands forms [Pd(triphosphine)(CH{sub 3}CN)](BF{sub 4}){sub 2} complexes that are all water soluble with the exception of [Pd(IPNetpE)(CH{sub 3}-CN)](BF{sub 4}){sub 2}. The labile acetonitrile ligands are easily substituted by triethylphosphine to form [Pd(triphosphine)-(PEt{sub 3})](BF{sub 4}){sub 2} complexes. The triethylphosphine complexes undergo quasi-reversible two-electron reductions while the corresponding acetonitrile complexes undergo two, closely spaced, irreversible, one-electron reductions. [Pd-(HOPetpE)(CH{sub 3}CN)](BF{sub 4}){sub 2} and [Pd(etpEPO)(CH{sub 3}CN)](BF{sub 4}){sub 2} are catalysts for the electrochemical reduction of CO{sub 2} to CO in both dimethylformamide and buffered aqueous solutions. Kinetic studies are reported for [Pd-(HOPetpE)(CH{sub 3}CN)](BF{sub 4}){sub 2} in dimethylformamide.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 457087
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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