Journal article

Publication year: 2010

Pages: 9450-9459

Journal: Inorganic Chemistry

Volume number: 49

Issue number: 20

ISSN: 0020-1669

Open access status: Green

DOI Link: https://doi.org/10.1021/ic101138u

Publisher: American Chemical Society

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 (η(1)) bound superoxo-Cu(II) complex [TMG(3)trenCuO(2)](+) (where TMG(3)tren is 1,1,1-tris[2-[N(2)-(1,1,3,3-tetramethylguanidino)]ethyl]amine). The spectral features of [TMG(3)trenCuO(2)](+) 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 [TMG(3)trenCuO(2)](+) eliminates antiferromagnetic coupling between the copper(II) and the superoxide, while the significant superoxo π*(σ) character of the copper dz(2) orbital leads to its ferromagnetically coupled, triplet, ground state.

Harvard Citation style: Woertink, J., Tian, L., Maiti, D., Lucas, H., Himes, R., Karlin, K., 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), pp. 9450-9459. https://doi.org/10.1021/ic101138u

APA Citation style: Woertink, J., Tian, L., Maiti, D., Lucas, H., Himes, R., Karlin, K., Neese, F., Würtele, C., Holthausen, M., Bill, E., Sundermeyer, J., Schindler, S., & Solomon, E. (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. https://doi.org/10.1021/ic101138u