Spectroscopic and Computational Studies of an End-on Bound Superoxo-Cu(II) 
Complex: Geometric and Electronic Factors That Determine the Ground State

Woertink, Julia S.; Tian, Li; Maiti, Debabrata; Lucas, Heather R.; Himes, Richard A.; Karlin, Kenneth D.; Neese, Frank; Würtele, Christian; Holthausen, Max C.; Bill, Eckhard; Sundermeyer, Jörg; Schindler, Siegfried; Solomon, Edward I.

doi:10.1021/ic101138u

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Spectroscopic and Computational Studies of an End-on Bound Superoxo-Cu(II) Complex: Geometric and Electronic Factors That Determine the Ground State

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Bill, Eckhard
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Woertink, J. S., Tian, L., Maiti, D., Lucas, H. R., Himes, R. A., Karlin, K. D., et al. (2010). Spectroscopic and Computational Studies of an End-on Bound Superoxo-Cu(II) Complex: Geometric and Electronic Factors That Determine the Ground State. Inorganic Chemistry, 49(20), 9450-9459. doi:10.1021/ic101138u.

Cite as: https://hdl.handle.net/21.11116/0000-0008-0FBF-2

Abstract

A variety of techniques including absorption, magnetic circular dichroism (MCD), variable-temperature, variable-field MCD (VTVH-MCD), and resonance Raman (rR) spectroscopies are combined with density functional theory (DFT) calculations to elucidate the electronic structure of the end-on (η¹) bound superoxo-Cu(II) complex [TMG₃trenCuO₂]⁺ (where TMG₃tren is 1,1,1-tris[2-[N²-(1,1,3,3-tetramethylguanidino)]ethyl]amine). The spectral features of [TMG₃trenCuO₂]⁺ are assigned, including the first definitive assignment of a superoxo intraligand transition in a metal-superoxo complex, and a detailed description of end-on superoxo-Cu(II) bonding is developed. The lack of overlap between the two magnetic orbitals of [TMG₃trenCuO₂]⁺ eliminates antiferromagnetic coupling between the copper(II) and the superoxide, while the significant superoxo π*σ character of the copper d_z² orbital leads to its ferromagnetically coupled, triplet, ground state.