Synthesis and characterization of palladium and nickel complexes with positively charged triphosphine ligands and their use as electrochemical CO2-reduction catalysts

Alex Miedaner; Bruce C. Noll; Daniel L. DuBois

doi:10.1021/om970519c

Synthesis and characterization of palladium and nickel complexes with positively charged triphosphine ligands and their use as electrochemical CO₂-reduction catalysts

Alex Miedaner, Bruce C. Noll, Daniel L. DuBois

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

31 Citations (Scopus)

Abstract

The synthesis and characterization of [M(Bu₃P⁺etpE)Br](BF₄)₂ (where M = Ni or Pd and Bu₃P⁺etpE = [(Bu₃PCH₂CH₂)P(CH₂CH ₂PEt₂)₂]⁺) and [M(etpPBu₃⁺)Br]Br(BF₄)₄ (where M = Ni or Pd and etpPBu₃⁺ = {PhP[CH₂CH₂P(CH₂CH₂PBu ₃)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 catalytic reaction are reported.

Original language	English
Pages (from-to)	5779-5791
Number of pages	13
Journal	Organometallics
Volume	16
Issue number	26
DOIs	https://doi.org/10.1021/om970519c
Publication status	Published - Dec 23 1997

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Synthesis and characterization of palladium and nickel complexes with positively charged triphosphine ligands and their use as electrochemical CO2-reduction catalysts",

abstract = "The synthesis and characterization of [M(Bu3P+etpE)Br](BF4)2 (where M = Ni or Pd and Bu3P+etpE = [(Bu3PCH2CH2)P(CH2CH 2PEt2)2]+) and [M(etpPBu3+)Br]Br(BF4)4 (where M = Ni or Pd and etpPBu3+ = {PhP[CH2CH2P(CH2CH2PBu 3)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 catalytic reaction are reported.",

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AU - Miedaner, Alex

AU - Noll, Bruce C.

AU - DuBois, Daniel L.

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N2 - The synthesis and characterization of [M(Bu3P+etpE)Br](BF4)2 (where M = Ni or Pd and Bu3P+etpE = [(Bu3PCH2CH2)P(CH2CH 2PEt2)2]+) and [M(etpPBu3+)Br]Br(BF4)4 (where M = Ni or Pd and etpPBu3+ = {PhP[CH2CH2P(CH2CH2PBu 3)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 catalytic reaction are reported.

AB - The synthesis and characterization of [M(Bu3P+etpE)Br](BF4)2 (where M = Ni or Pd and Bu3P+etpE = [(Bu3PCH2CH2)P(CH2CH 2PEt2)2]+) and [M(etpPBu3+)Br]Br(BF4)4 (where M = Ni or Pd and etpPBu3+ = {PhP[CH2CH2P(CH2CH2PBu 3)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 catalytic reaction are reported.

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