Electrochemical reduction of CO 2 to CO catalyzed by a bimetallic palladium complex

James W. Raebiger; Jeffrey W. Turner; Bruce C. Noll; Calvin J. Curtis; Alex Miedaner; Brian Cox; Daniel L. DuBois

doi:10.1021/om060228g

Electrochemical reduction of CO ₂ to CO catalyzed by a bimetallic palladium complex

James W. Raebiger, Jeffrey W. Turner, Bruce C. Noll, Calvin J. Curtis, Alex Miedaner, Brian Cox, Daniel L. DuBois

Pacific Northwest National Laboratory

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

104 Citations (Scopus)

Abstract

The bis(triphosphine) ligand C ₆H ₄{P[CH ₂CH ₂CH ₂P(C ₆H ₁₁) ₂] ₂} ₂, m-(triphos) ₂ (1), is synthesized by the reaction of m-bis(phosphino)benzene with 4 equiv of vinyldicyclohexylphosphine. Reaction of 1 with 2 equiv of [Pd(CH ₃CN) ₄](BF ₄) ₂ results in the formation of the bimetallic complex {m-(triphos) ₂-[Pd(CH ₃CN)] ₂}(BF ₄) ₄ (2). A structural study of 2 confirms the presence of two [Pd(triphosphine)-(CH ₃CN)] ²⁺ substituents at the meta positions of a benzene ring. Complex 2 catalyzes the electrochemical reduction of CO ₂ to CO in acidic dimethylformamide solutions. The kinetics of this reaction have been studied, and the reaction is 0.5 order in catalyst and first order in CO ₂. This catalyst exhibits catalytic rates comparable to that of its monometallic analogues. Significantly higher turnover numbers are observed for 2 than observed previously for monometallic, bimetallic, and dendritic complexes of this class of catalysts.

Original language	English
Pages (from-to)	3345-3351
Number of pages	7
Journal	Organometallics
Volume	25
Issue number	14
DOIs	https://doi.org/10.1021/om060228g
Publication status	Published - Jul 3 2006

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{16d2751995764aa2be70370dac3b6097,

title = "Electrochemical reduction of CO 2 to CO catalyzed by a bimetallic palladium complex",

abstract = "The bis(triphosphine) ligand C 6H 4{P[CH 2CH 2CH 2P(C 6H 11) 2] 2} 2, m-(triphos) 2 (1), is synthesized by the reaction of m-bis(phosphino)benzene with 4 equiv of vinyldicyclohexylphosphine. Reaction of 1 with 2 equiv of [Pd(CH 3CN) 4](BF 4) 2 results in the formation of the bimetallic complex {m-(triphos) 2-[Pd(CH 3CN)] 2}(BF 4) 4 (2). A structural study of 2 confirms the presence of two [Pd(triphosphine)-(CH 3CN)] 2+ substituents at the meta positions of a benzene ring. Complex 2 catalyzes the electrochemical reduction of CO 2 to CO in acidic dimethylformamide solutions. The kinetics of this reaction have been studied, and the reaction is 0.5 order in catalyst and first order in CO 2. This catalyst exhibits catalytic rates comparable to that of its monometallic analogues. Significantly higher turnover numbers are observed for 2 than observed previously for monometallic, bimetallic, and dendritic complexes of this class of catalysts.",

author = "Raebiger, {James W.} and Turner, {Jeffrey W.} and Noll, {Bruce C.} and Curtis, {Calvin J.} and Alex Miedaner and Brian Cox and DuBois, {Daniel L.}",

year = "2006",

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T1 - Electrochemical reduction of CO 2 to CO catalyzed by a bimetallic palladium complex

AU - Raebiger, James W.

AU - Turner, Jeffrey W.

AU - Noll, Bruce C.

AU - Curtis, Calvin J.

AU - Miedaner, Alex

AU - Cox, Brian

AU - DuBois, Daniel L.

PY - 2006/7/3

Y1 - 2006/7/3

N2 - The bis(triphosphine) ligand C 6H 4{P[CH 2CH 2CH 2P(C 6H 11) 2] 2} 2, m-(triphos) 2 (1), is synthesized by the reaction of m-bis(phosphino)benzene with 4 equiv of vinyldicyclohexylphosphine. Reaction of 1 with 2 equiv of [Pd(CH 3CN) 4](BF 4) 2 results in the formation of the bimetallic complex {m-(triphos) 2-[Pd(CH 3CN)] 2}(BF 4) 4 (2). A structural study of 2 confirms the presence of two [Pd(triphosphine)-(CH 3CN)] 2+ substituents at the meta positions of a benzene ring. Complex 2 catalyzes the electrochemical reduction of CO 2 to CO in acidic dimethylformamide solutions. The kinetics of this reaction have been studied, and the reaction is 0.5 order in catalyst and first order in CO 2. This catalyst exhibits catalytic rates comparable to that of its monometallic analogues. Significantly higher turnover numbers are observed for 2 than observed previously for monometallic, bimetallic, and dendritic complexes of this class of catalysts.

AB - The bis(triphosphine) ligand C 6H 4{P[CH 2CH 2CH 2P(C 6H 11) 2] 2} 2, m-(triphos) 2 (1), is synthesized by the reaction of m-bis(phosphino)benzene with 4 equiv of vinyldicyclohexylphosphine. Reaction of 1 with 2 equiv of [Pd(CH 3CN) 4](BF 4) 2 results in the formation of the bimetallic complex {m-(triphos) 2-[Pd(CH 3CN)] 2}(BF 4) 4 (2). A structural study of 2 confirms the presence of two [Pd(triphosphine)-(CH 3CN)] 2+ substituents at the meta positions of a benzene ring. Complex 2 catalyzes the electrochemical reduction of CO 2 to CO in acidic dimethylformamide solutions. The kinetics of this reaction have been studied, and the reaction is 0.5 order in catalyst and first order in CO 2. This catalyst exhibits catalytic rates comparable to that of its monometallic analogues. Significantly higher turnover numbers are observed for 2 than observed previously for monometallic, bimetallic, and dendritic complexes of this class of catalysts.

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