Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst

McLoughlin, Elizabeth A.; Matson, Benjamin D.; Sarangi, Ritimukta; Waymouth, Robert M.

doi:10.1021/acs.inorgchem.9b03230

Title: Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst

Full Record
Other Related Research

Abstract

Electrochemical and chemical studies reveal that the amido complex (PNH_xP)Fe(CO)(H)(X) (FeN 1, x = 0, X = 0; Fe(H)(NH) 2, x = 1, X = H; PNHP = bis[2-(diisopropylphosphino)ethyl]amine) is active for the electrocatalytic oxidation of isopropanol. At room temperature, the amido FeN 1 dehydrogenates isopropanol to form acetone. The resulting amino hydride complex Fe(H)(NH) 2 is subsequently oxidized by one electron at a low potential (–0.74 V versus ferrocene/ferrocenium, Fc^o/+) in tetrahydrofuran. In the presence of strong base (phosphazene base P₂-Et, Et-N = P₂(dma)₅, P2), this oxidation process becomes a two-electron, two-proton process that regenerates FeN 1. FeN 1 is active for the electrooxidation of isopropanol in the presence of strong base (i.e., P2) with an onset potential near –1 V versus Fc^o/+. By cyclic voltammetry, fast turnover frequencies of 1.7 s^–1 for isopropanol oxidation are achieved with FeN 1. Lastly, controlled potential electrolysis studies confirm that the product of isopropanol electrooxidation is acetone, generated with high Faradaic efficiency (~100%).

Authors:

^[1];

^[2];

^[3];

^[1]

Stanford Univ., CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Publication Date:: Mon Dec 30 00:00:00 EST 2019

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)

OSTI Identifier:: 1594172

Alternate Identifier(s):: OSTI ID: 1605284

Grant/Contract Number:: SC0018168; CHE-1213403; AC02-76SF00515; 2017-4-Waymouth

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 59; Journal Issue: 2; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Alcohols; Anions; Catalysts; Tetrahydrofurans; Oxidation

Citation Formats


                    McLoughlin, Elizabeth A., Matson, Benjamin D., Sarangi, Ritimukta, and Waymouth, Robert M. Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.inorgchem.9b03230.

Copy to clipboard


                    McLoughlin, Elizabeth A., Matson, Benjamin D., Sarangi, Ritimukta, & Waymouth, Robert M. Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst.  United States.  https://doi.org/10.1021/acs.inorgchem.9b03230

Copy to clipboard


                    McLoughlin, Elizabeth A., Matson, Benjamin D., Sarangi, Ritimukta, and Waymouth, Robert M. Mon .  
"Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst".  United States.  https://doi.org/10.1021/acs.inorgchem.9b03230.  https://www.osti.gov/servlets/purl/1594172.

Copy to clipboard


                    
@article{osti_1594172,

  title        = {Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst},

  author       = {McLoughlin, Elizabeth A. and Matson, Benjamin D. and Sarangi, Ritimukta and Waymouth, Robert M.},

  abstractNote = {Electrochemical and chemical studies reveal that the amido complex (PNHxP)Fe(CO)(H)(X) (FeN 1, x = 0, X = 0; Fe(H)(NH) 2, x = 1, X = H; PNHP = bis[2-(diisopropylphosphino)ethyl]amine) is active for the electrocatalytic oxidation of isopropanol. At room temperature, the amido FeN 1 dehydrogenates isopropanol to form acetone. The resulting amino hydride complex Fe(H)(NH) 2 is subsequently oxidized by one electron at a low potential (–0.74 V versus ferrocene/ferrocenium, Fco/+) in tetrahydrofuran. In the presence of strong base (phosphazene base P2-Et, Et-N = P2(dma)5, P2), this oxidation process becomes a two-electron, two-proton process that regenerates FeN 1. FeN 1 is active for the electrooxidation of isopropanol in the presence of strong base (i.e., P2) with an onset potential near –1 V versus Fco/+. By cyclic voltammetry, fast turnover frequencies of 1.7 s–1 for isopropanol oxidation are achieved with FeN 1. Lastly, controlled potential electrolysis studies confirm that the product of isopropanol electrooxidation is acetone, generated with high Faradaic efficiency (~100%).},

  doi          = {10.1021/acs.inorgchem.9b03230},

  journal      = {Inorganic Chemistry},

  number       = 2,

  volume       = 59,

  place        = {United States},

  year         = {Mon Dec 30 00:00:00 EST 2019},

  month        = {Mon Dec 30 00:00:00 EST 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.inorgchem.9b03230

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 13 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Diiron Dithiolate Hydrides Complemented with Proton‐Responsive Phosphine–Amine Ligands

Journal Article Carlson, Michaela R. ; Gilbert‐Wilson, Ryan ; Gray, Danielle R. ; ... - European Journal of Inorganic Chemistry

The reaction of Fe ₂ (pdt)(CO) ₆ with two equivalents of Ph ₂ PC ₆ H ₄ NH ₂ (PNH ₂ ) affords the amido hydride HFe ₂ (pdt)(CO) ₂ (PNH ₂ )(PNH) {[H 1 H] ⁰ , pdt ^2– = CH ₂ (CH ₂ S ^– ) ₂ }. Isolated intermediates in this conversion include Fe ₂ (pdt)(CO) ₅ (κ ¹ ‐PNH ₂ ) and Fe ₂ (pdt)(CO) ₄ (κ ² ‐PNH ₂ ). X‐ray crystallographic analysis of [H 1 H] ⁰ shows that the chelating amino/amido–phosphine ligands occupy trans ‐dibasal positions. The ³¹ P NMR spectrum indicates thatmore »« less
Cited by 6
https://doi.org/10.1002/ejic.201700474
Hydrosilylation of an Iron(IV) Nitride Complex

Journal Article Valdez-Moreira, Juan A. ; Millikan, Sean P. ; Gao, Xinfeng ; ... - Inorganic Chemistry

The nitride ligand in iron(IV) complex PhB(MesIm)₃Fe≡N reacts with excess H₃SiPh to afford PhB(MesIm)₃Fe(μ-H)₃(SiHPh) as the major product, which has been structurally and spectroscopically characterized. Bulkier silane H_aSiPh₂ provides iron(II) amido complex PhB(MesIm)₃FeN(H)(SiHPh₂) as the initial product of the reaction, with excess H₂SiPh₂ affording diamagnetic PhB(MesIm)₃Fe(μ-H)₃(SiPh₂) as the major product. Lastly, unobserved iron(II) hydride PhB(MesIm)₃Fe–H is implicated as an intermediate in this reaction, as suggested by the results of the reaction between iron(II) amido PhB(MesIm)₃FeN(H)^tBu and H₃SiPh, which provides PhB(MesIm)₃Fe(H)(μ-H)₂(Si(NH^tBu)Ph) as the sole product.
Cited by 4
https://doi.org/10.1021/acs.inorgchem.9b02831

Full Text Available
Structural, thermal, spectroscopic and magnetic studies of the (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}[Fe {sub x}V{sub 1-x}(HPO{sub 3}){sub 2}] (x = 0.26, 0.52, 0.74) solid solution

Journal Article Cisneros, Jose L ; Fernandez-Armas, Sergio ; Mesa, Jose L ; ... - Materials Research Bulletin

The (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}[Fe {sub x}V{sub 1-x}(HPO{sub 3}){sub 2}] (x = 0.26, 0.52 0.74) compounds have been obtained by mild solvothermal conditions in the form of micro-crystalline powder with brown color. The crystal structures were refined by X-ray powder diffraction data using the Rietveld method. The compounds crystallize in the monoclinic system, space group P2/c with the unit-cell parameters, a = 9.262(5) A, b = 8.823(5) A, c = 9.714(6) A, {beta} = 120.84(3){sup o}; a = 9.245(1) A, b = 8.823(1) A, c = 9.698(1)A, {beta} = 120.80(1){sup o} and, a = 9.254(4)A, b = 8.822(4)A, cmore »« less
https://doi.org/10.1016/j.materresbull.2006.03.035
Effect of Redox Active Ligands on the Electrochemical Properties of Manganese Tricarbonyl Complexes

Journal Article Matson, Benjamin D. ; McLoughlin, Elizabeth A. ; Armstrong, Keith C. ; ... - Inorganic Chemistry

The synthesis, structural characterization, and electrochemical behavior of the neutral Mn(azpy)(CO)₃(Br) 4 (azpy = 2-phenylazopyridine) complex is reported and compared with its structural analogue Mn(bipy)(CO)₃(Br) 1 (bipy = 2,2'-bipyridine). 4 exhibits reversible two-electron reduction at a mild potential (-0.93 V vs Fc^+/0 in acetonitrile) in contrast to 1, which exhibits two sequential one-electron reductions at -1.68 V and -1.89 V vs Fc^+/0 in acetonitrile. The key electronic structure differences between 1 and 4 that lead to disparate electrochemical properties are investigated using a combination of Mn-K-edge X-ray absorption spectroscopy (XAS), Mn-Kβ X-ray emission spectroscopy (XES), and density functional theory (DFT)more »« less
Cited by 9
https://doi.org/10.1021/acs.inorgchem.9b00652

Full Text Available
Reactions of (Cp(CO) sub 2 Fe double bond CHAr) sup + (Ar = p-C sub 6 H sub 4 OMe) with O double bond N-Ar prime (Ar prime = C sub 6 H sub 5 , p-C sub 6 H sub 4 NMe sub 2 ) and PhN double bond NPh

Journal Article Peng, Wei-Jun ; Gamble, A S ; Templeton, J L ; ... - Inorganic Chemistry; (USA)

Organometallic products formed from the reaction of an electrophilic iron carbene complex with nitrosoarenes or azobenzene reflect net insertion of the ArN{double bond}X moiety into the Fe{double bond}CHAr bond. Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} and Cp(CO){sub 2}FeN(Ph)-N(Ph){double bond}CHAr{sup +} (Ar = p-C{sub 6}H{sub 4}OMe, Ar{prime} = p-C{sub 6}H{sub 4}NMe{sub 2}) have been isolated and spectroscopically characterized; the crystal structure of Cp(CO){sub 2}Fe-O-N(Ph){double bond}CHAr{sup +} is reported. Exposure of acetone solutions of Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} or Cp(CO){sub 2}FeN(Ph)-N(Ph){double bond}char{sup +} to light yields imine products Ar{prime}N{double bond}CHAr or PhN{double bond}CHAr, respectively. There is no evidence to support the formation of themore »« less
https://doi.org/10.1021/ic00328a024

Similar Records