Hydrogen Atom or Proton Coupled Electron Transfer? C-H Bond Activation by Transition-Metal Oxides

Carlo Alberto Gaggioli; Joachim Sauer; Laura Gagliardi

doi:10.1021/jacs.9b04006

Hydrogen Atom or Proton Coupled Electron Transfer? C-H Bond Activation by Transition-Metal Oxides

Carlo Alberto Gaggioli, Joachim Sauer, Laura Gagliardi

Chemistry (Twin Cities)

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

25 Scopus citations

Abstract

The C-H bond activation in oxidative dehydrogenation of propane by heterobimetallic oxide clusters (first-row transition metals), deposited on the zirconium oxide node of the NU-1000 metal organic framework, was investigated by multireference wave function theory. The redox-active part of the systems studied has the composition (CoO)(MO)(OH)₂ with M = Ti, Mn, Fe, Co, Ni, Cu, Zn. In this series, the energy of H transfer from propane to the metal oxide (?E) varies from -26 kcal/mol for M = Cu, Zn to 85 kcal/mol for M = Ti. This is accompanied by a change in the mechanism from hydrogen atom transfer, M²⁺(dⁿ) O^- → M²⁺(dⁿ) OH^-, for M = Cu, Zn to proton coupled electron transfer, M^m+(dⁿ) O^2- → M^(m-1)+(dⁿ⁺¹) OH^-, for M = Ni, Co, Fe, Mn, Ti. Whereas for M = Ni (?E = -13 kcal/mol) Ni^+III is reduced to Ni^+II, for M = Co, Fe, Mn (?E = 1, 10, 6 kcal/mol, respectively) it is Co^+III that is reduced to Co^+II. For M = Ti, Ti maintains its +IV oxidation state and Co^+II is reduced to Co^+I

Original language	English (US)
Pages (from-to)	14603-14611
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	141
Issue number	37
DOIs	https://doi.org/10.1021/jacs.9b04006
State	Published - Sep 18 2019

Bibliographical note

Funding Information:
This work was supported by the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702), and by the German Research Foundation (DFG). The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. J.S. has been supported by the “Fonds der Chemischen Industrie”.

Publisher Copyright:
Copyright © 2019 American Chemical Society.

PubMed: MeSH publication types

Journal Article

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Publisher link

10.1021/jacs.9b04006

Find It

Find It at U of M Libraries

Cite this

@article{1ed3cf7eba504d928a3426ac90e06947,

title = "Hydrogen Atom or Proton Coupled Electron Transfer? C-H Bond Activation by Transition-Metal Oxides",

abstract = "The C-H bond activation in oxidative dehydrogenation of propane by heterobimetallic oxide clusters (first-row transition metals), deposited on the zirconium oxide node of the NU-1000 metal organic framework, was investigated by multireference wave function theory. The redox-active part of the systems studied has the composition (CoO)(MO)(OH)2 with M = Ti, Mn, Fe, Co, Ni, Cu, Zn. In this series, the energy of H transfer from propane to the metal oxide (?E) varies from -26 kcal/mol for M = Cu, Zn to 85 kcal/mol for M = Ti. This is accompanied by a change in the mechanism from hydrogen atom transfer, M2+(dn) O- → M2+(dn) OH-, for M = Cu, Zn to proton coupled electron transfer, Mm+(dn) O2- → M(m-1)+(dn+1) OH-, for M = Ni, Co, Fe, Mn, Ti. Whereas for M = Ni (?E = -13 kcal/mol) Ni+III is reduced to Ni+II, for M = Co, Fe, Mn (?E = 1, 10, 6 kcal/mol, respectively) it is Co+III that is reduced to Co+II. For M = Ti, Ti maintains its +IV oxidation state and Co+II is reduced to Co+I",

author = "Gaggioli, {Carlo Alberto} and Joachim Sauer and Laura Gagliardi",

note = "Funding Information: This work was supported by the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702), and by the German Research Foundation (DFG). The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. J.S. has been supported by the “Fonds der Chemischen Industrie”. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = sep,

day = "18",

doi = "10.1021/jacs.9b04006",

language = "English (US)",

volume = "141",

pages = "14603--14611",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "37",

}

TY - JOUR

T1 - Hydrogen Atom or Proton Coupled Electron Transfer? C-H Bond Activation by Transition-Metal Oxides

AU - Gaggioli, Carlo Alberto

AU - Sauer, Joachim

AU - Gagliardi, Laura

N1 - Funding Information: This work was supported by the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702), and by the German Research Foundation (DFG). The authors acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing computational resources. J.S. has been supported by the “Fonds der Chemischen Industrie”. Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/9/18

Y1 - 2019/9/18

N2 - The C-H bond activation in oxidative dehydrogenation of propane by heterobimetallic oxide clusters (first-row transition metals), deposited on the zirconium oxide node of the NU-1000 metal organic framework, was investigated by multireference wave function theory. The redox-active part of the systems studied has the composition (CoO)(MO)(OH)2 with M = Ti, Mn, Fe, Co, Ni, Cu, Zn. In this series, the energy of H transfer from propane to the metal oxide (?E) varies from -26 kcal/mol for M = Cu, Zn to 85 kcal/mol for M = Ti. This is accompanied by a change in the mechanism from hydrogen atom transfer, M2+(dn) O- → M2+(dn) OH-, for M = Cu, Zn to proton coupled electron transfer, Mm+(dn) O2- → M(m-1)+(dn+1) OH-, for M = Ni, Co, Fe, Mn, Ti. Whereas for M = Ni (?E = -13 kcal/mol) Ni+III is reduced to Ni+II, for M = Co, Fe, Mn (?E = 1, 10, 6 kcal/mol, respectively) it is Co+III that is reduced to Co+II. For M = Ti, Ti maintains its +IV oxidation state and Co+II is reduced to Co+I

AB - The C-H bond activation in oxidative dehydrogenation of propane by heterobimetallic oxide clusters (first-row transition metals), deposited on the zirconium oxide node of the NU-1000 metal organic framework, was investigated by multireference wave function theory. The redox-active part of the systems studied has the composition (CoO)(MO)(OH)2 with M = Ti, Mn, Fe, Co, Ni, Cu, Zn. In this series, the energy of H transfer from propane to the metal oxide (?E) varies from -26 kcal/mol for M = Cu, Zn to 85 kcal/mol for M = Ti. This is accompanied by a change in the mechanism from hydrogen atom transfer, M2+(dn) O- → M2+(dn) OH-, for M = Cu, Zn to proton coupled electron transfer, Mm+(dn) O2- → M(m-1)+(dn+1) OH-, for M = Ni, Co, Fe, Mn, Ti. Whereas for M = Ni (?E = -13 kcal/mol) Ni+III is reduced to Ni+II, for M = Co, Fe, Mn (?E = 1, 10, 6 kcal/mol, respectively) it is Co+III that is reduced to Co+II. For M = Ti, Ti maintains its +IV oxidation state and Co+II is reduced to Co+I

UR - http://www.scopus.com/inward/record.url?scp=85072353340&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85072353340&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b04006

DO - 10.1021/jacs.9b04006

M3 - Article

C2 - 31432676

AN - SCOPUS:85072353340

SN - 0002-7863

VL - 141

SP - 14603

EP - 14611

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 37

ER -

Hydrogen Atom or Proton Coupled Electron Transfer? C-H Bond Activation by Transition-Metal Oxides

Abstract

Bibliographical note

PubMed: MeSH publication types

UN SDGs

Publisher link

Find It

Other files and links

Fingerprint

Cite this