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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.

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.

SUBMITTER: Woertink JS 

PROVIDER: S-EPMC2963092 | biostudies-literature | 2010 Oct

REPOSITORIES: biostudies-literature

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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.

Woertink Julia S JS   Tian Li L   Maiti Debabrata D   Lucas Heather R HR   Himes Richard A RA   Karlin Kenneth D KD   Neese Frank F   Würtele Christian C   Holthausen Max C MC   Bill Eckhard E   Sundermeyer Jörg J   Schindler Siegfried S   Solomon Edward I EI  

Inorganic chemistry 20101001 20

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, includ  ...[more]