Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt–Copper Complexes
Abstract
Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. Finally by contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.
- Authors:
-
- Univ. of Minnesota, Minneapolis, MN (United States)
- Univ. of Chicago, Argonne, IL (United States)
- Max Planck Inst. für Chemische Energiekonversion, Stiftstraβe (Germany)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1370855
- Grant/Contract Number:
- SC0012702; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 23; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington; 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; catalysis (heterogeneous); materials and chemistry by design; synthesis (novel materials)
Citation Formats
Eisenhart, Reed J., Carlson, Rebecca K., Clouston, Laura J., Young, Victor G., Chen, Yu-Sheng, Bill, Eckhard, Gagliardi, Laura, and Lu, Connie C. Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt–Copper Complexes. United States: N. p., 2015.
Web. doi:10.1021/acs.inorgchem.5b01950.
Eisenhart, Reed J., Carlson, Rebecca K., Clouston, Laura J., Young, Victor G., Chen, Yu-Sheng, Bill, Eckhard, Gagliardi, Laura, & Lu, Connie C. Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt–Copper Complexes. United States. https://doi.org/10.1021/acs.inorgchem.5b01950
Eisenhart, Reed J., Carlson, Rebecca K., Clouston, Laura J., Young, Victor G., Chen, Yu-Sheng, Bill, Eckhard, Gagliardi, Laura, and Lu, Connie C. Mon .
"Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt–Copper Complexes". United States. https://doi.org/10.1021/acs.inorgchem.5b01950. https://www.osti.gov/servlets/purl/1370855.
@article{osti_1370855,
title = {Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt–Copper Complexes},
author = {Eisenhart, Reed J. and Carlson, Rebecca K. and Clouston, Laura J. and Young, Victor G. and Chen, Yu-Sheng and Bill, Eckhard and Gagliardi, Laura and Lu, Connie C.},
abstractNote = {Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. Finally by contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.},
doi = {10.1021/acs.inorgchem.5b01950},
journal = {Inorganic Chemistry},
number = 23,
volume = 54,
place = {United States},
year = {Mon Nov 09 00:00:00 EST 2015},
month = {Mon Nov 09 00:00:00 EST 2015}
}
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Works referenced in this record:
Copper Active Sites in Biology
journal, January 2014
- Solomon, Edward I.; Heppner, David E.; Johnston, Esther M.
- Chemical Reviews, Vol. 114, Issue 7
Copper-Dioxygen Complexes. Inorganic and Bioinorganic Perspectives
journal, May 1994
- Kitajima, Nobumasa; Moro-oka, Yoshihiko
- Chemical Reviews, Vol. 94, Issue 3
Reactivity of Dioxygen−Copper Systems
journal, February 2004
- Lewis, Elizabeth A.; Tolman, William B.
- Chemical Reviews, Vol. 104, Issue 2
A Cytochrome c Oxidase Model Catalyzes Oxygen to Water Reduction Under Rate-Limiting Electron Flux
journal, March 2007
- Collman, J. P.; Devaraj, N. K.; Decreau, R. A.
- Science, Vol. 315, Issue 5818, p. 1565-1568
A Synthetic Model of the Mn3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II
journal, August 2011
- Kanady, J. S.; Tsui, E. Y.; Day, M. W.
- Science, Vol. 333, Issue 6043
Oxidative Group Transfer to a Triiron Complex to Form a Nucleophilic μ 3 -Nitride, [Fe 3 (μ 3 -N)] −
journal, March 2011
- Powers, Tamara M.; Fout, Alison R.; Zheng, Shao-Liang
- Journal of the American Chemical Society, Vol. 133, Issue 10
A synthetic Mn4Ca-cluster mimicking the oxygen-evolving center of photosynthesis
journal, May 2015
- Zhang, C.; Chen, C.; Dong, H.
- Science, Vol. 348, Issue 6235
Reactivity of Hydride Bridges in High-Spin [3M–3(μ-H)] Clusters (M = Fe II , Co II )
journal, August 2015
- Lee, Yousoon; Anderton, Kevin J.; Sloane, Forrest T.
- Journal of the American Chemical Society, Vol. 137, Issue 33
Dinitrogen Activation Upon Reduction of a Triiron(II) Complex
journal, December 2014
- Lee, Yousoon; Sloane, Forrest T.; Blondin, Geneviève
- Angewandte Chemie International Edition, Vol. 54, Issue 5
Catalytic Applications of Early/Late Heterobimetallic Complexes
journal, January 2012
- Cooper, Benjamin G.; Napoline, J. Wesley; Thomas, Christine M.
- Catalysis Reviews, Vol. 54, Issue 1
Evaluating the Effect of Catalyst Nuclearity in Ni-Catalyzed Alkyne Cyclotrimerizations
journal, June 2015
- Pal, Sudipta; Uyeda, Christopher
- Journal of the American Chemical Society, Vol. 137, Issue 25
On the Mechanism of Palladium-Catalyzed Aromatic C−H Oxidation
journal, October 2010
- Powers, David C.; Xiao, Daphne Y.; Geibel, Matthias A. L.
- Journal of the American Chemical Society, Vol. 132, Issue 41
Direct Spectroscopic Characterization of a Transitory Dirhodium Donor-Acceptor Carbene Complex
journal, September 2013
- Kornecki, K. P.; Briones, J. F.; Boyarskikh, V.
- Science, Vol. 342, Issue 6156
Base Metal Catalysts for Photochemical C–H Borylation That Utilize Metal–Metal Cooperativity
journal, October 2013
- Mazzacano, Thomas J.; Mankad, Neal P.
- Journal of the American Chemical Society, Vol. 135, Issue 46
A Heterobimetallic Mechanism for C–H Borylation Elucidated from Experimental and Computational Data
journal, May 2015
- Parmelee, Sean R.; Mazzacano, Thomas J.; Zhu, Yaqun
- ACS Catalysis, Vol. 5, Issue 6
Cuprophilicity: Spectroscopic and Structural Evidence for Cu−Cu Bonding Interactions in Luminescent Dinuclear Copper(I) Complexes with Bridging Diphosphane Ligands
journal, November 2000
- Che, Chi-Ming; Mao, Zhong; Miskowski, Vincent M.
- Angewandte Chemie, Vol. 39, Issue 22
A data-intensive re-evaluation of semibridging carbonyl ligands
journal, January 2015
- Parmelee, Sean R.; Mankad, Neal P.
- Dalton Transactions, Vol. 44, Issue 39
Deprotonation of uncharged transition-metal dihydrogen complexes with copper alkoxides, characterization of the heterometallic complexes (PR3)xMHyCu(PR3) (M = iron, tungsten), and x-ray crystal structure of (PEtPh2)3FeH3Cu(PEtPh2)
journal, March 1991
- Van der Sluys, Lori Stepan; Miller, M. M.; Kubas, Gregory J.
- Journal of the American Chemical Society, Vol. 113, Issue 7
The First Structural Characterisation of a Group 2 Metal Alkylperoxide Complex: Comments on the Cleavage of Dioxygen by Magnesium Alkyl Complexes
journal, October 2003
- Bailey, Philip J.; Coxall, Robert A.; Dick, Caroline M.
- Chemistry - A European Journal, Vol. 9, Issue 19
Role of the Metal in the Bonding and Properties of Bimetallic Complexes Involving Manganese, Iron, and Cobalt
journal, November 2013
- Tereniak, Stephen J.; Carlson, Rebecca K.; Clouston, Laura J.
- Journal of the American Chemical Society, Vol. 136, Issue 5
Experimental distinction of elements with similar atomic number using anomalous dispersion (δ synthesis): an application of synchrotron radiation in crystal structure analysis
journal, August 1990
- Wulf, R.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 46, Issue 8
GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013
- Toby, Brian H.; Von Dreele, Robert B.
- Journal of Applied Crystallography, Vol. 46, Issue 2
Magnetochemistry-Advances in Theory and Experimentation
book, January 2007
- O'Connor, Charles J.
- Progress in Inorganic Chemistry, Vol. 29
MOLCAS 7: The Next Generation
journal, January 2010
- Aquilante, Francesco; De Vico, Luca; Ferré, Nicolas
- Journal of Computational Chemistry, Vol. 31, Issue 1
Relativistic atomic natural orbital type basis sets for the alkaline and alkaline-earth atoms applied to the ground-state potentials for the corresponding dimers
journal, December 2003
- Roos, Björn O.; Veryazov, Valera; Widmark, Per-Olof
- Theoretical Chemistry Accounts, Vol. 111, Issue 2-6
New Relativistic ANO Basis Sets for Transition Metal Atoms
journal, July 2005
- Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke
- The Journal of Physical Chemistry A, Vol. 109, Issue 29
Relativistic Douglas-Kroll-Hess theory: Relativistic DKH theory
journal, June 2011
- Reiher, Markus
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1
Unbiased auxiliary basis sets for accurate two-electron integral approximations
journal, September 2007
- Aquilante, Francesco; Lindh, Roland; Bondo Pedersen, Thomas
- The Journal of Chemical Physics, Vol. 127, Issue 11
Multiconfiguration perturbation theory with imaginary level shift
journal, August 1997
- Forsberg, Niclas; Malmqvist, Per-Åke
- Chemical Physics Letters, Vol. 274, Issue 1-3
Reaching the Maximum Multiplicity of the Covalent Chemical Bond
journal, February 2007
- Roos, Björn O.; Borin, Antonio C.; Gagliardi, Laura
- Angewandte Chemie International Edition, Vol. 46, Issue 9
Structural Comparison of Copper(I) and Copper(II) Complexes with Tris(2-pyridylmethyl)amine Ligand
journal, November 2010
- Eckenhoff, William T.; Pintauer, Tomislav
- Inorganic Chemistry, Vol. 49, Issue 22
Nonprecious Metal Catalysts for Fuel Cell Applications: Electrochemical Dioxygen Activation by a Series of First Row Transition Metal Tris(2-pyridylmethyl)amine Complexes
journal, March 2012
- Ward, Ashleigh L.; Elbaz, Lior; Kerr, John B.
- Inorganic Chemistry, Vol. 51, Issue 8
Molecular Heme−Cyanide−Copper Bridged Assemblies: Linkage Isomerism, Trends in ν CN Values, and Relation to the Heme- a 3 /Cu B Site in Cyanide-Inhibited Heme−Copper Oxidases
journal, September 1998
- Lim, Booyong S.; Holm, R. H.
- Inorganic Chemistry, Vol. 37, Issue 19
Zero-field splitting in pentacoordinate Co(II) complexes
journal, November 2013
- Rajnák, C.; Titiš, J.; Šalitroš, I.
- Polyhedron, Vol. 65
Reversible reaction of dioxygen (and carbon monoxide) with a copper(I) complex. X-ray structures of relevant mononuclear Cu(I) precursor adducts and the trans-(.mu.-1,2-peroxo)dicopper(II) product
journal, April 1993
- Tyeklar, Zoltan; Jacobson, Richard R.; Wei, Ning
- Journal of the American Chemical Society, Vol. 115, Issue 7
Tetragonal vs. trigonal coordination in copper(II) complexes with tripod ligands: structures and properties of [Cu(C21H24N4)Cl]PF6 and [Cu(C18H18N4)Cl]PF6
journal, November 1982
- Karlin, Kenneth D.; Hayes, Jon C.; Juen, Shi.
- Inorganic Chemistry, Vol. 21, Issue 11
Comparative study of the catalytic oxidation of catechols by copper(II) complexes of tripodal ligands
journal, January 1995
- Malachowski, Mitchell R.; Huynh, Hong B.; Tomlinson, Laura J.
- Journal of the Chemical Society, Dalton Transactions, Issue 1
Crystal structure and electronic properties of ammine[tris(2-aminoethyl)amine]copper(II) diperchlorate and potassium penta-amminecopper(II) tris(hexafluorophosphate)
journal, January 1980
- Duggan, Mary; Ray, Noel; Hathaway, Brian
- Journal of the Chemical Society, Dalton Transactions, Issue 8
Configuring Bonds between First-Row Transition Metals
journal, October 2015
- Eisenhart, Reed J.; Clouston, Laura J.; Lu, Connie C.
- Accounts of Chemical Research, Vol. 48, Issue 11
Can Multiconfigurational Self-Consistent Field Theory and Density Functional Theory Correctly Predict the Ground State of Metal–Metal-Bonded Complexes?
journal, August 2015
- Carlson, Rebecca K.; Odoh, Samuel O.; Tereniak, Stephen J.
- Journal of Chemical Theory and Computation, Vol. 11, Issue 9
Works referencing / citing this record:
Heteronuclear assembly of Ni–Cu dithiolato complexes: synthesis, structures, and reactivity studies
journal, January 2017
- Chu, Xiaoxiao; Xu, Xin; Su, Hao
- Inorganic Chemistry Frontiers, Vol. 4, Issue 4
Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities
journal, October 2018
- Vogiatzis, Konstantinos D.; Polynski, Mikhail V.; Kirkland, Justin K.
- Chemical Reviews, Vol. 119, Issue 4