Electrochemical reduction of CO2 catalyzed by a dinuclear palladium complex containing a bridging hexaphosphine ligand: Evidence for cooperativity

Bryan D. Steffey; Calvin J. Curtis; Daniel L. DuBois

Electrochemical reduction of CO2 catalyzed by a dinuclear palladium complex containing a bridging hexaphosphine ligand: Evidence for cooperativity

Bryan D. Steffey, Calvin J. Curtis, Daniel L. DuBois

Pacific Northwest National Laboratory

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Abstract

The complexes [Pd₂(CH₃CN)₂(eHTP)](BF₄)₄ and [Pd₂(PEt₃)₂(eHTP)](BF₄)₄ (where eHTP is bis(bis((diethylphosphino)ethyl)phosphino))methane, (Et₂PCH₂CH₂)₂PCH ₂P(CH₂CH₂PEt₂)₂) were prepared and characterized. [Pd₂(CH₃CN)₂(eHTP)](BF₄)₄ catalyzes the electrochemical reduction of CO₂ to CO in acidic dimethylformamide solutions. The rate of this reaction exhibits a biphasic dependence on acid, with a first-order dependence at low acid concentrations and zero-order dependence at acid concentrations greater than 0.06 M. At high acid concentrations the rate-limiting step is first order in catalyst and first order in CO₂. When compared to the kinetic properties of previously studied mononuclear complexes, these data suggest both palladium atoms are involved in CO₂ reduction. The closely related complex [Pd₂(PEt₃)₂(eHTP)](BF₄)₄ undergoes two reversible two-electron reductions. The mixed-valence intermediate resulting from the first two-electron reduction is unstable and undergoes rapid decomposition.

Original language	English
Pages (from-to)	4937-4943
Number of pages	7
Journal	Organometallics
Volume	14
Issue number	10
Publication status	Published - 1995

ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

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title = "Electrochemical reduction of CO2 catalyzed by a dinuclear palladium complex containing a bridging hexaphosphine ligand: Evidence for cooperativity",

abstract = "The complexes [Pd2(CH3CN)2(eHTP)](BF4)4 and [Pd2(PEt3)2(eHTP)](BF4)4 (where eHTP is bis(bis((diethylphosphino)ethyl)phosphino))methane, (Et2PCH2CH2)2PCH 2P(CH2CH2PEt2)2) were prepared and characterized. [Pd2(CH3CN)2(eHTP)](BF4)4 catalyzes the electrochemical reduction of CO2 to CO in acidic dimethylformamide solutions. The rate of this reaction exhibits a biphasic dependence on acid, with a first-order dependence at low acid concentrations and zero-order dependence at acid concentrations greater than 0.06 M. At high acid concentrations the rate-limiting step is first order in catalyst and first order in CO2. When compared to the kinetic properties of previously studied mononuclear complexes, these data suggest both palladium atoms are involved in CO2 reduction. The closely related complex [Pd2(PEt3)2(eHTP)](BF4)4 undergoes two reversible two-electron reductions. The mixed-valence intermediate resulting from the first two-electron reduction is unstable and undergoes rapid decomposition.",

author = "Steffey, {Bryan D.} and Curtis, {Calvin J.} and DuBois, {Daniel L.}",

year = "1995",

language = "English",

volume = "14",

pages = "4937--4943",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "10",

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TY - JOUR

T1 - Electrochemical reduction of CO2 catalyzed by a dinuclear palladium complex containing a bridging hexaphosphine ligand

T2 - Evidence for cooperativity

AU - Steffey, Bryan D.

AU - Curtis, Calvin J.

AU - DuBois, Daniel L.

PY - 1995

Y1 - 1995

N2 - The complexes [Pd2(CH3CN)2(eHTP)](BF4)4 and [Pd2(PEt3)2(eHTP)](BF4)4 (where eHTP is bis(bis((diethylphosphino)ethyl)phosphino))methane, (Et2PCH2CH2)2PCH 2P(CH2CH2PEt2)2) were prepared and characterized. [Pd2(CH3CN)2(eHTP)](BF4)4 catalyzes the electrochemical reduction of CO2 to CO in acidic dimethylformamide solutions. The rate of this reaction exhibits a biphasic dependence on acid, with a first-order dependence at low acid concentrations and zero-order dependence at acid concentrations greater than 0.06 M. At high acid concentrations the rate-limiting step is first order in catalyst and first order in CO2. When compared to the kinetic properties of previously studied mononuclear complexes, these data suggest both palladium atoms are involved in CO2 reduction. The closely related complex [Pd2(PEt3)2(eHTP)](BF4)4 undergoes two reversible two-electron reductions. The mixed-valence intermediate resulting from the first two-electron reduction is unstable and undergoes rapid decomposition.

AB - The complexes [Pd2(CH3CN)2(eHTP)](BF4)4 and [Pd2(PEt3)2(eHTP)](BF4)4 (where eHTP is bis(bis((diethylphosphino)ethyl)phosphino))methane, (Et2PCH2CH2)2PCH 2P(CH2CH2PEt2)2) were prepared and characterized. [Pd2(CH3CN)2(eHTP)](BF4)4 catalyzes the electrochemical reduction of CO2 to CO in acidic dimethylformamide solutions. The rate of this reaction exhibits a biphasic dependence on acid, with a first-order dependence at low acid concentrations and zero-order dependence at acid concentrations greater than 0.06 M. At high acid concentrations the rate-limiting step is first order in catalyst and first order in CO2. When compared to the kinetic properties of previously studied mononuclear complexes, these data suggest both palladium atoms are involved in CO2 reduction. The closely related complex [Pd2(PEt3)2(eHTP)](BF4)4 undergoes two reversible two-electron reductions. The mixed-valence intermediate resulting from the first two-electron reduction is unstable and undergoes rapid decomposition.

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