Electrocatalytic Oxidation of Alcohol with Cobalt Triphosphine Complexes

Spencer P. Heins; Patrick E. Schneider; Amy L. Speelman; Sharon Hammes-Schiffer; Aaron M. Appel

doi:10.1021/acscatal.1c00781

Electrocatalytic Oxidation of Alcohol with Cobalt Triphosphine Complexes

Spencer P. Heins, Patrick E. Schneider, Amy L. Speelman, Sharon Hammes-Schiffer, Aaron M. Appel

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

14 Scopus citations

Abstract

Coordination of the tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (P3) to cobalt forms [(CH3CN)2CoIIP3](BF4)2 (CoIIP3). In the presence of the Brönsted base iPr2EtN, CoIIP3 electrocatalytically oxidizes benzyl alcohol (BnOH) to benzaldehyde at an applied potential of -630 mV vs Fc+/0 with a TON of 19.9. In a noncatalytic reaction with excess BnOH and iPr2EtN, CoIIP3 is reduced by one electron to [(CH3CN)2CoIP3]BF4 (CoIP3) with concomitant formation of half an equivalent of benzaldehyde. This stoichiometric oxidation of BnOH suggests electron transfer occurs between intermediate cobalt species and starting CoIIP3. Kinetics and computational studies support an unfavorable alcohol binding preequilibrium step followed by favorable deprotonation of the bound alcohol.

Original language	English (US)
Pages (from-to)	6384-6389
Number of pages	6
Journal	ACS Catalysis
Volume	11
Issue number	11
DOIs	https://doi.org/10.1021/acscatal.1c00781
State	Published - Jun 4 2021
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry

Keywords

alcohol oxidation
catalysis
catalyst design
cobalt
electrocatalysis
electrocatalyst
electrooxidation

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10.1021/acscatal.1c00781

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title = "Electrocatalytic Oxidation of Alcohol with Cobalt Triphosphine Complexes",

abstract = "Coordination of the tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (P3) to cobalt forms [(CH3CN)2CoIIP3](BF4)2 (CoIIP3). In the presence of the Br{\"o}nsted base iPr2EtN, CoIIP3 electrocatalytically oxidizes benzyl alcohol (BnOH) to benzaldehyde at an applied potential of -630 mV vs Fc+/0 with a TON of 19.9. In a noncatalytic reaction with excess BnOH and iPr2EtN, CoIIP3 is reduced by one electron to [(CH3CN)2CoIP3]BF4 (CoIP3) with concomitant formation of half an equivalent of benzaldehyde. This stoichiometric oxidation of BnOH suggests electron transfer occurs between intermediate cobalt species and starting CoIIP3. Kinetics and computational studies support an unfavorable alcohol binding preequilibrium step followed by favorable deprotonation of the bound alcohol.",

keywords = "alcohol oxidation, catalysis, catalyst design, cobalt, electrocatalysis, electrocatalyst, electrooxidation",

author = "Heins, {Spencer P.} and Schneider, {Patrick E.} and Speelman, {Amy L.} and Sharon Hammes-Schiffer and Appel, {Aaron M.}",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = jun,

day = "4",

doi = "10.1021/acscatal.1c00781",

language = "English (US)",

volume = "11",

pages = "6384--6389",

journal = "ACS Catalysis",

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T1 - Electrocatalytic Oxidation of Alcohol with Cobalt Triphosphine Complexes

AU - Heins, Spencer P.

AU - Schneider, Patrick E.

AU - Speelman, Amy L.

AU - Hammes-Schiffer, Sharon

AU - Appel, Aaron M.

PY - 2021/6/4

Y1 - 2021/6/4

N2 - Coordination of the tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (P3) to cobalt forms [(CH3CN)2CoIIP3](BF4)2 (CoIIP3). In the presence of the Brönsted base iPr2EtN, CoIIP3 electrocatalytically oxidizes benzyl alcohol (BnOH) to benzaldehyde at an applied potential of -630 mV vs Fc+/0 with a TON of 19.9. In a noncatalytic reaction with excess BnOH and iPr2EtN, CoIIP3 is reduced by one electron to [(CH3CN)2CoIP3]BF4 (CoIP3) with concomitant formation of half an equivalent of benzaldehyde. This stoichiometric oxidation of BnOH suggests electron transfer occurs between intermediate cobalt species and starting CoIIP3. Kinetics and computational studies support an unfavorable alcohol binding preequilibrium step followed by favorable deprotonation of the bound alcohol.

AB - Coordination of the tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (P3) to cobalt forms [(CH3CN)2CoIIP3](BF4)2 (CoIIP3). In the presence of the Brönsted base iPr2EtN, CoIIP3 electrocatalytically oxidizes benzyl alcohol (BnOH) to benzaldehyde at an applied potential of -630 mV vs Fc+/0 with a TON of 19.9. In a noncatalytic reaction with excess BnOH and iPr2EtN, CoIIP3 is reduced by one electron to [(CH3CN)2CoIP3]BF4 (CoIP3) with concomitant formation of half an equivalent of benzaldehyde. This stoichiometric oxidation of BnOH suggests electron transfer occurs between intermediate cobalt species and starting CoIIP3. Kinetics and computational studies support an unfavorable alcohol binding preequilibrium step followed by favorable deprotonation of the bound alcohol.

KW - alcohol oxidation

KW - catalysis

KW - catalyst design

KW - cobalt

KW - electrocatalysis

KW - electrocatalyst

KW - electrooxidation

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U2 - 10.1021/acscatal.1c00781

DO - 10.1021/acscatal.1c00781

M3 - Article

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SN - 2155-5435

VL - 11

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JO - ACS Catalysis

JF - ACS Catalysis

IS - 11

ER -

Electrocatalytic Oxidation of Alcohol with Cobalt Triphosphine Complexes

Abstract

All Science Journal Classification (ASJC) codes

Keywords

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