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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

Title
Spectroscopic and computational studies of an end-on bound superoxo-Cu(II) complex: Geometric and electronic factors that determine the ground state
Authors
Woertink J.S.Tian L.Maiti D.Lucas H.R.Himes R.A.Karlin K.D.Neese F.Wurtele C.Holthausen M.C.Bill E.Sundermeyer J.Schindler S.Solomon E.I.
Ewha Authors
Kenneth D. Karlin
Issue Date
2010
Journal Title
Inorganic Chemistry
ISSN
0020-1669JCR Link
Citation
vol. 49, no. 20, pp. 9450 - 9459
Indexed
SCI; SCIE; SCOPUS WOS scopus
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 3trenCuO 2] + (where TMG 3tren 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 metalsuperoxo 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 3trenCuO 2] + eliminates antiferromagnetic coupling between the copper(II) and the superoxide, while the significant superoxo π * δ character of the copper dz 2 orbital leads to its ferromagnetically coupled, triplet, ground state. © 2010 American Chemical Society.
DOI
10.1021/ic101138u
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일반대학원 > 바이오융합과학과 > Journal papers
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