Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt-Copper Complexes

Reed J. Eisenhart, Rebecca K. Carlson, Laura J. Clouston, Victor G. Young, Yu Sheng Chen, Eckhard Bill, Laura Gagliardi, Connie C. Lu

Research output: Contribution to journalArticle

6 Citations (Scopus)

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. By contrast, no covalent Co-Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.

Original languageEnglish (US)
Pages (from-to)11330-11338
Number of pages9
JournalInorganic Chemistry
Volume54
Issue number23
DOIs
StatePublished - Nov 9 2015

Fingerprint

Cobalt
Electronic structure
Copper
cobalt
electronic structure
copper
Oxidation
oxidation
Electrons
electrons
X ray scattering
coordination polymers
Absorption spectroscopy
Cyclic voltammetry
acetonitrile
magnetic measurement
Amines
Paramagnetic resonance
reagents
electron paramagnetic resonance

Cite this

Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt-Copper Complexes. / Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.; Young, Victor G.; Chen, Yu Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C.

In: Inorganic Chemistry, Vol. 54, No. 23, 09.11.2015, p. 11330-11338.

Research output: Contribution to journalArticle

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. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 23. pp. 11330-11338.
@article{476c1e77d296406fa4fab69418af952c,
title = "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. By contrast, no covalent Co-Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.",
author = "Eisenhart, {Reed J.} and Carlson, {Rebecca K.} and Clouston, {Laura J.} and Young, {Victor G.} and Chen, {Yu Sheng} and Eckhard Bill and Laura Gagliardi and Lu, {Connie C.}",
year = "2015",
month = "11",
day = "9",
doi = "10.1021/acs.inorgchem.5b01950",
language = "English (US)",
volume = "54",
pages = "11330--11338",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "23",

}

TY - JOUR

T1 - Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt-Copper Complexes

AU - Eisenhart, Reed J.

AU - Carlson, Rebecca K.

AU - Clouston, Laura J.

AU - Young, Victor G.

AU - Chen, Yu Sheng

AU - Bill, Eckhard

AU - Gagliardi, Laura

AU - Lu, Connie C.

PY - 2015/11/9

Y1 - 2015/11/9

N2 - 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. By contrast, no covalent Co-Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.

AB - 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. By contrast, no covalent Co-Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.

UR - http://www.scopus.com/inward/record.url?scp=84947241214&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84947241214&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.5b01950

DO - 10.1021/acs.inorgchem.5b01950

M3 - Article

C2 - 26551246

AN - SCOPUS:84947241214

VL - 54

SP - 11330

EP - 11338

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 23

ER -