skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O 2 activation by non-adiabatic oxidative addition to a single metal center]

Abstract

A chromium(I) dinitrogen complex reacts rapidly with O 2 to form the mononuclear dioxo complex [Tp tBu,MeCr V(O) 2] (Tp tBu,Me=hydrotris(3- tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [Tp tBu,MeCr III(S 2)]. The transformation of the putative peroxo intermediate [Tp tBu,MeCr III(O 2)] (S= 3/ 2) into [Tp tBu,MeCr V(O) 2] (S= 1/ 2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(Tp tBu,MeCr) 2(μ-O) 2] exists, mechanistic experiments suggest that O 2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.

Authors:
 [1];  [1];  [1]
  1. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1342854
Grant/Contract Number:  
FG02-92ER14273
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 54; Journal Issue: 49; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ab initio calculations; chromium; dioxygen activation; spin-forbidden reactions; sulfur

Citation Formats

Akturk, Eser S., Yap, Glenn P. A., and Theopold, Klaus H. Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]. United States: N. p., 2015. Web. doi:10.1002/anie.201508777.
Akturk, Eser S., Yap, Glenn P. A., & Theopold, Klaus H. Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]. United States. doi:10.1002/anie.201508777.
Akturk, Eser S., Yap, Glenn P. A., and Theopold, Klaus H. Fri . "Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]". United States. doi:10.1002/anie.201508777. https://www.osti.gov/servlets/purl/1342854.
@article{osti_1342854,
title = {Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center]},
author = {Akturk, Eser S. and Yap, Glenn P. A. and Theopold, Klaus H.},
abstractNote = {A chromium(I) dinitrogen complex reacts rapidly with O2 to form the mononuclear dioxo complex [TptBu,MeCrV(O)2] (TptBu,Me=hydrotris(3-tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [TptBu,MeCrIII(S2)]. The transformation of the putative peroxo intermediate [TptBu,MeCrIII(O2)] (S=3/2) into [TptBu,MeCrV(O)2] (S=1/2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(TptBu,MeCr)2(μ-O)2] exists, mechanistic experiments suggest that O2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.},
doi = {10.1002/anie.201508777},
journal = {Angewandte Chemie (International Edition)},
number = 49,
volume = 54,
place = {United States},
year = {2015},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Molecular structures of a) 3 and b) 4 (30 % probability level). Selected interatomic distances (Å) and angles(°): a) Cr–O1, 1.6007(19); Cr–O2, 1.6050(19); Cr–N1, 2. 216(2); Cr–N3, 2.265(2); Cr–N5(1.979(2); O1–Cr–O2, 108.14(10); b) Cr–S1, 2.3220(15); Cr–S2, 2. 2398(16); S1–S2, 2.0565(18), Cr–Navg, 2.109; S1–Cr–S2, 53.55(6).

Save / Share:

Works referenced in this record:

Spectroscopic and Theoretical Studies of Transition Metal Oxides and Dioxygen Complexes
journal, December 2009

  • Gong, Yu; Zhou, Mingfei; Andrews, Lester
  • Chemical Reviews, Vol. 109, Issue 12
  • DOI: 10.1021/cr900185x

Understanding the reactivity of transition metal complexes involving multiple spin states
journal, March 2003


Reactivity of Dioxygen−Copper Systems
journal, February 2004

  • Lewis, Elizabeth A.; Tolman, William B.
  • Chemical Reviews, Vol. 104, Issue 2
  • DOI: 10.1021/cr020633r

Quintuple Bond Reactivity toward Group 16 and 17 Elements: Addition vs Insertion
journal, December 2012

  • Tamne, Emmanuel Sobgwi; Noor, Awal; Qayyum, Sadaf
  • Inorganic Chemistry, Vol. 52, Issue 1
  • DOI: 10.1021/ic3020805

A Tale of Two Isomers: A Stable Phenyl Hydride and a High-Spin (S=3) Benzene Complex of Chromium
journal, September 2007

  • Monillas, Wesley H.; Yap, Glenn P. A.; Theopold, Klaus H.
  • Angewandte Chemie International Edition, Vol. 46, Issue 35
  • DOI: 10.1002/anie.200701933

Spin Surface Crossing in Chromium-Mediated Olefin Epoxidation with O 2
journal, March 2002

  • Hess, James S.; Leelasubcharoen, Somying; Rheingold, Arnold L.
  • Journal of the American Chemical Society, Vol. 124, Issue 11
  • DOI: 10.1021/ja0167553

Can Spin State Change Slow Organometallic Reactions?
journal, November 1995

  • Detrich, Jennifer L.; Reinaud, Olivia M.; Rheingold, Arnold L.
  • Journal of the American Chemical Society, Vol. 117, Issue 47
  • DOI: 10.1021/ja00152a015

Metal-Dioxygen Complexes: A Perspective
journal, May 1994

  • Klotz, Irving M.; Kurtz, Donald M.
  • Chemical Reviews, Vol. 94, Issue 3
  • DOI: 10.1021/cr00027a001

Peroxo and Superoxo Complexes of Chromium, Molybdenum, and Tungsten
journal, May 1994

  • Dickman, Michael H.; Pope, Michael T.
  • Chemical Reviews, Vol. 94, Issue 3
  • DOI: 10.1021/cr00027a002

Synthesis and crystal structure of (.eta.5-C5Me5)2Cr2S5 containing an unusual bridging disulfur ligand .eta.1-(.mu.-S,S)
journal, March 1982

  • Brunner, Henri; Wachter, Joachim; Guggolz, Ernst
  • Journal of the American Chemical Society, Vol. 104, Issue 6
  • DOI: 10.1021/ja00370a065

Mechanism-based design of labile precursors for chromium( i ) chemistry
journal, January 2015

  • Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.
  • Chemical Communications, Vol. 51, Issue 84
  • DOI: 10.1039/C5CC05993C

A Tale of Two Isomers: A Stable Phenyl Hydride and a High-Spin (S=3) Benzene Complex of Chromium
journal, September 2007

  • Monillas, Wesley H.; Yap, Glenn P. A.; Theopold, Klaus H.
  • Angewandte Chemie, Vol. 119, Issue 35
  • DOI: 10.1002/ange.200701933

Spin forbidden chemical reactions of transition metal compounds. New ideas and new computational challenges
journal, November 2002

  • Poli, Rinaldo; Harvey, Jeremy N.
  • Chemical Society Reviews, Vol. 32, Issue 1
  • DOI: 10.1039/b200675h

Chromium Dioxide Cation OCrO + in the Gas Phase:  Structure, Electronic States, and the Reactivity with Hydrogen and Hydrocarbons 1
journal, January 1996

  • Fiedler, Andreas; Kretzschmar, Ilona; Schröder, Detlef
  • Journal of the American Chemical Society, Vol. 118, Issue 41
  • DOI: 10.1021/ja960157k

Two-State Reactivity as a New Concept in Organometallic Chemistry §
journal, March 2000

  • Schröder, Detlef; Shaik, Sason; Schwarz, Helmut
  • Accounts of Chemical Research, Vol. 33, Issue 3
  • DOI: 10.1021/ar990028j

Mehrfachbindungen zwischen hauptgruppenelementen und übergangsmetallen
journal, April 1985

  • Herrmann, Wolfgang A.; Rohrmann, Jürgen; Nöth, Heinrich
  • Journal of Organometallic Chemistry, Vol. 284, Issue 2
  • DOI: 10.1016/0022-328X(85)87212-0

C−H Bond Activations by Metal Oxo Compounds
journal, February 2010

  • Gunay, Ahmet; Theopold, Klaus H.
  • Chemical Reviews, Vol. 110, Issue 2
  • DOI: 10.1021/cr900269x

The Direct Oxidative Addition of O 2 to a Mononuclear Cr(I) Complex Is Spin Forbidden
journal, October 2013

  • Dai, Fang; Yap, Glenn P. A.; Theopold, Klaus H.
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja408357x

Variable character of O--O and M--O bonding in side-on ( 2) 1:1 metal complexes of O2
journal, March 2003

  • Cramer, C. J.; Tolman, W. B.; Theopold, K. H.
  • Proceedings of the National Academy of Sciences, Vol. 100, Issue 7
  • DOI: 10.1073/pnas.0535926100

Chemistry of [CpCr(CO)3]2. Synthesis of Cp2Cr2(CO)4S, Cp2Cr2(CO)4S2, and Cp2Cr2(CO)5S2. Crystal structure and reactivity of Cp2Cr2(CO)4S2 and Cp2Cr2(CO)5S2
journal, May 1987

  • Goh, Lai Yoong.; Hambley, Trevor W.; Robertson, Glen B.
  • Organometallics, Vol. 6, Issue 5
  • DOI: 10.1021/om00148a024

Structure and Spectroscopy of Copper−Dioxygen Complexes
journal, February 2004

  • Mirica, Liviu M.; Ottenwaelder, Xavier; Stack, T. Daniel P.
  • Chemical Reviews, Vol. 104, Issue 2
  • DOI: 10.1021/cr020632z

Sulphur chromium complexes: syntheses and crystal structures of (η 5 C 5 H 5 ) 2 Cr 2 (CO) 4 S and (η 5 -C 5 H 5 ) 2 Cr 2 (CO) 5 S 2
journal, January 1983

  • Goh, Lai Yoong; Hambley, Trevor W.; Robertson, Glen B.
  • J. Chem. Soc., Chem. Commun., Issue 23
  • DOI: 10.1039/C39830001458

A Structurally Characterized Chromium(III) Superoxide Complex Features “Side-on” Bonding
journal, July 2002


Dioxygen Activation at Monovalent Nickel
journal, July 2007

  • Kieber-Emmons, Matthew T.; Riordan, Charles G.
  • Accounts of Chemical Research, Vol. 40, Issue 7
  • DOI: 10.1021/ar700043n

A Structurally Characterized Chromium(III) Superoxide Complex Features “Side-on” Bonding
journal, July 2002


Dioxygen Activation at Mononuclear Nonheme Iron Active Sites:  Enzymes, Models, and Intermediates
journal, February 2004

  • Costas, Miquel; Mehn, Mark P.; Jensen, Michael P.
  • Chemical Reviews, Vol. 104, Issue 2
  • DOI: 10.1021/cr020628n

The singlet and triplet states of phenyl cation. A hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces
journal, April 1998

  • Harvey, Jeremy N.; Aschi, Massimiliano; Schwarz, Helmut
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 99, Issue 2
  • DOI: 10.1007/s002140050309

Sulfurization and Selenization of the Halfsandwich Nitrosylmetal Complexes Cp*M(CO)2NO (M = Cr, Mo) and Cp*M(NO)I2 (M = Mo, W)
journal, November 1993

  • Herberhold, Max; Jin, Guo-Xin; Rheingold, Arnold L.
  • Zeitschrift für Naturforschung B, Vol. 48, Issue 11
  • DOI: 10.1515/znb-1993-1106

Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen
journal, February 1998

  • Herrmann, Wolfgang A.; Wachter, Wolfgang M.; Kühn, Fritz E.
  • Journal of Organometallic Chemistry, Vol. 553, Issue 1-2
  • DOI: 10.1016/s0022-328x(97)00607-4

    Works referencing / citing this record:

    Dioxygen Activation at Monovalent Nickel
    journal, July 2007

    • Kieber-Emmons, Matthew T.; Riordan, Charles G.
    • Accounts of Chemical Research, Vol. 40, Issue 7
    • DOI: 10.1021/ar700043n

    Synthesis and crystal structure of (.eta.5-C5Me5)2Cr2S5 containing an unusual bridging disulfur ligand .eta.1-(.mu.-S,S)
    journal, March 1982

    • Brunner, Henri; Wachter, Joachim; Guggolz, Ernst
    • Journal of the American Chemical Society, Vol. 104, Issue 6
    • DOI: 10.1021/ja00370a065

    Understanding the kinetics of spin-forbidden chemical reactions
    journal, January 2007

    • Harvey, Jeremy N.
    • Phys. Chem. Chem. Phys., Vol. 9, Issue 3
    • DOI: 10.1039/b614390c

    Two-State Reactivity as a New Concept in Organometallic Chemistry §
    journal, March 2000

    • Schröder, Detlef; Shaik, Sason; Schwarz, Helmut
    • Accounts of Chemical Research, Vol. 33, Issue 3
    • DOI: 10.1021/ar990028j

    The singlet and triplet states of phenyl cation. A hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces
    journal, April 1998

    • Harvey, Jeremy N.; Aschi, Massimiliano; Schwarz, Helmut
    • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 99, Issue 2
    • DOI: 10.1007/s002140050309

    Variable character of O--O and M--O bonding in side-on ( 2) 1:1 metal complexes of O2
    journal, March 2003

    • Cramer, C. J.; Tolman, W. B.; Theopold, K. H.
    • Proceedings of the National Academy of Sciences, Vol. 100, Issue 7
    • DOI: 10.1073/pnas.0535926100

    Peroxo and Superoxo Complexes of Chromium, Molybdenum, and Tungsten
    journal, May 1994

    • Dickman, Michael H.; Pope, Michael T.
    • Chemical Reviews, Vol. 94, Issue 3
    • DOI: 10.1021/cr00027a002

    Metal-Dioxygen Complexes: A Perspective
    journal, May 1994

    • Klotz, Irving M.; Kurtz, Donald M.
    • Chemical Reviews, Vol. 94, Issue 3
    • DOI: 10.1021/cr00027a001

    A Tale of Two Isomers: A Stable Phenyl Hydride and a High-Spin (S=3) Benzene Complex of Chromium
    journal, September 2007

    • Monillas, Wesley H.; Yap, Glenn P. A.; Theopold, Klaus H.
    • Angewandte Chemie International Edition, Vol. 46, Issue 35
    • DOI: 10.1002/anie.200701933

    Spin forbidden chemical reactions of transition metal compounds. New ideas and new computational challenges
    journal, November 2002

    • Poli, Rinaldo; Harvey, Jeremy N.
    • Chemical Society Reviews, Vol. 32, Issue 1
    • DOI: 10.1039/b200675h

    Rhodium Complexes Promoting C−O Bond Formation in Reactions with Oxygen: The Role of Superoxo Species
    journal, March 2017

    • Vilella-Arribas, Laia; García-Melchor, Max; Balcells, David
    • Chemistry - A European Journal, Vol. 23, Issue 22
    • DOI: 10.1002/chem.201605959

    Dioxygen Activation at Mononuclear Nonheme Iron Active Sites:  Enzymes, Models, and Intermediates
    journal, February 2004

    • Costas, Miquel; Mehn, Mark P.; Jensen, Michael P.
    • Chemical Reviews, Vol. 104, Issue 2
    • DOI: 10.1021/cr020628n

    Spectroscopic and Theoretical Studies of Transition Metal Oxides and Dioxygen Complexes
    journal, December 2009

    • Gong, Yu; Zhou, Mingfei; Andrews, Lester
    • Chemical Reviews, Vol. 109, Issue 12
    • DOI: 10.1021/cr900185x

    CCDC 1414460: Experimental Crystal Structure Determination: FUYTAW : (1,1',1''-boranetriyltris(3-t-butyl-5-methyl-1H-pyrazole))-dioxo-chromium(v)
    dataset, July 2015

    • Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/cc1jgvrl

    A Tale of Two Isomers: A Stable Phenyl Hydride and a High-Spin (S=3) Benzene Complex of Chromium
    journal, September 2007

    • Monillas, Wesley H.; Yap, Glenn P. A.; Theopold, Klaus H.
    • Angewandte Chemie, Vol. 119, Issue 35
    • DOI: 10.1002/ange.200701933

    Chromium Dioxide Cation OCrO + in the Gas Phase:  Structure, Electronic States, and the Reactivity with Hydrogen and Hydrocarbons 1
    journal, January 1996

    • Fiedler, Andreas; Kretzschmar, Ilona; Schröder, Detlef
    • Journal of the American Chemical Society, Vol. 118, Issue 41
    • DOI: 10.1021/ja960157k

    Structure and Spectroscopy of Copper−Dioxygen Complexes
    journal, February 2004

    • Mirica, Liviu M.; Ottenwaelder, Xavier; Stack, T. Daniel P.
    • Chemical Reviews, Vol. 104, Issue 2
    • DOI: 10.1021/cr020632z

    The Direct Oxidative Addition of O 2 to a Mononuclear Cr(I) Complex Is Spin Forbidden
    journal, October 2013

    • Dai, Fang; Yap, Glenn P. A.; Theopold, Klaus H.
    • Journal of the American Chemical Society, Vol. 135, Issue 45
    • DOI: 10.1021/ja408357x

    Chemistry of [CpCr(CO)3]2. Synthesis of Cp2Cr2(CO)4S, Cp2Cr2(CO)4S2, and Cp2Cr2(CO)5S2. Crystal structure and reactivity of Cp2Cr2(CO)4S2 and Cp2Cr2(CO)5S2
    journal, May 1987

    • Goh, Lai Yoong.; Hambley, Trevor W.; Robertson, Glen B.
    • Organometallics, Vol. 6, Issue 5
    • DOI: 10.1021/om00148a024

    Spin Surface Crossing in Chromium-Mediated Olefin Epoxidation with O 2
    journal, March 2002

    • Hess, James S.; Leelasubcharoen, Somying; Rheingold, Arnold L.
    • Journal of the American Chemical Society, Vol. 124, Issue 11
    • DOI: 10.1021/ja0167553

    Can Spin State Change Slow Organometallic Reactions?
    journal, November 1995

    • Detrich, Jennifer L.; Reinaud, Olivia M.; Rheingold, Arnold L.
    • Journal of the American Chemical Society, Vol. 117, Issue 47
    • DOI: 10.1021/ja00152a015

    The Influence of Alkali Metal Ions on the Stability and Reactivity of Chromium(III) Superoxide Moieties Spanned by Siloxide Ligands
    journal, March 2019

    • Wind, Marie‐Louise; Hoof, Santina; Herwig, Christian
    • Chemistry – A European Journal, Vol. 25, Issue 22
    • DOI: 10.1002/chem.201900236

    Reactivity of Dioxygen−Copper Systems
    journal, February 2004

    • Lewis, Elizabeth A.; Tolman, William B.
    • Chemical Reviews, Vol. 104, Issue 2
    • DOI: 10.1021/cr020633r

    C−H Bond Activations by Metal Oxo Compounds
    journal, February 2010

    • Gunay, Ahmet; Theopold, Klaus H.
    • Chemical Reviews, Vol. 110, Issue 2
    • DOI: 10.1021/cr900269x

    Quintuple Bond Reactivity toward Group 16 and 17 Elements: Addition vs Insertion
    journal, December 2012

    • Tamne, Emmanuel Sobgwi; Noor, Awal; Qayyum, Sadaf
    • Inorganic Chemistry, Vol. 52, Issue 1
    • DOI: 10.1021/ic3020805

    Rhodium Complexes Promoting C−O Bond Formation in Reactions with Oxygen: The Role of Superoxo Species
    journal, March 2017

    • Vilella-Arribas, Laia; García-Melchor, Max; Balcells, David
    • Chemistry - A European Journal, Vol. 23, Issue 22
    • DOI: 10.1002/chem.201605959

    The Influence of Alkali Metal Ions on the Stability and Reactivity of Chromium(III) Superoxide Moieties Spanned by Siloxide Ligands
    journal, March 2019

    • Wind, Marie‐Louise; Hoof, Santina; Herwig, Christian
    • Chemistry – A European Journal, Vol. 25, Issue 22
    • DOI: 10.1002/chem.201900236

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.