Spectroscopic and Computational Studies of an End-on Bound Superoxo-Cu(II) Complex: Geometric and Electronic Factors That Determine the Ground State
In: Inorganic Chemistry, 2010
Online
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Zugriff:
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 d z 2 orbital leads to its ferromagnetically coupled, triplet, ground state.
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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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Autor/in / Beteiligte Person: | 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. |
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Zeitschrift: | Inorganic Chemistry, 2010 |
Veröffentlichung: | 2010 |
Medientyp: | academicJournal |
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