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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.

Authors
  • 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
Type
Published Article
Journal
Inorganic Chemistry
Publisher
American Chemical Society
Publication Date
Oct 18, 2010
Volume
49
Issue
20
Pages
9450–9459
Identifiers
DOI: 10.1021/ic101138u
PMID: 20857998
Source
Medline
License
Unknown

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.

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