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 [O2 activation by non-adiabatic oxidative addition to a single metal center]

Abstract

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.

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. https://doi.org/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. https://doi.org/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. https://doi.org/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

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

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

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


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

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

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

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

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

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

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

Mehrfachbindungen zwischen hauptgruppenelementen und übergangsmetallen
journal, June 1985

  • Herrmann, Wolfgang A.; Serrano, Ricardo; Küsthardt, Ulrich
  • Journal of Organometallic Chemistry, Vol. 287, Issue 3
  • DOI: 10.1016/0022-328x(85)80088-7

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

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


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

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

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

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

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

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

Spin-forbidden reactions: computational insight into mechanisms and kinetics: Spin-forbidden reactions
journal, June 2013

  • Harvey, Jeremy N.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1
  • DOI: 10.1002/wcms.1154

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


Dioxygen Activation at Monovalent Nickel
journal, October 2007


Oxygen complexes and oxygen activation by transition metals
journal, November 1988


Spin Forbidden Chemical Reactions of Transition Metal Compounds. New Ideas and New Computational Challenges
journal, April 2003


Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen
journal, August 1987

  • Hecht, Christian; Herdtweck, Eberhardt; Rohrmann, Jürgen
  • Journal of Organometallic Chemistry, Vol. 330, Issue 3
  • DOI: 10.1016/s0022-328x(00)99052-1

    Works referencing / citing this record:

    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.