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.

doi:10.1021/acs.inorgchem.5b01950

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

Journal Article · Mon Nov 09 00:00:00 EST 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b01950· OSTI ID:1370855

Eisenhart, Reed J. ^[1]; Carlson, Rebecca K. ^[1]; Clouston, Laura J. ^[1]; Young, Victor G. ^[1]; Chen, Yu-Sheng ^[2]; Bill, Eckhard ^[3]; Gagliardi, Laura ^[1]; Lu, Connie C. ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Chicago, Argonne, IL (United States)
Max Planck Inst. für Chemische Energiekonversion, Stiftstraβe (Germany)

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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; SC0012702

OSTI ID:: 1370855

Alternate ID(s):: OSTI ID: 1240192

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 23 Vol. 54; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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