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 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Electrochemical reduction of CO2 catalyzed by a dinuclear palladium complex containing a bridging hexaphosphine ligand : Evidence for cooperativity. / Steffey, Bryan D.; Curtis, Calvin J.; DuBois, Daniel L.
In: Organometallics, Vol. 14, No. 10, 1995, p. 4937-4943.Research output: Contribution to journal › Article
}
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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UR - http://www.scopus.com/inward/citedby.url?scp=0000358793&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0000358793
VL - 14
SP - 4937
EP - 4943
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 10
ER -