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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• 作者：Julia S. Woertink ; Li Tian ; Debabrata Maiti ; Heather R. Lucas ; Richard A. Himes ; Kenneth D. Karlin ; Frank Neese ; Christian Wrtele ; Max C. Holthausen ; Eckhard Bill ; Jrg Sundermeyer ; Siegfried Schindler
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：October 18, 2010
• 年：2010
• 卷：49
• 期：20
• 页码：9450-9459
• 全文大小：1030K
• 年卷期：v.49,no.20(October 18, 2010)
• ISSN：1520-510X

文摘

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 (η¹) bound superoxo-Cu(II) complex [TMG₃trenCuO₂]⁺ (where TMG₃tren is 1,1,1-tris[2-[N²-(1,1,3,3-tetramethylguanidino)]ethyl]amine). The spectral features of [TMG₃trenCuO₂]⁺ 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 [TMG₃trenCuO₂]⁺ eliminates antiferromagnetic coupling between the copper(II) and the superoxide, while the significant superoxo π*_σ character of the copper dz² orbital leads to its ferromagnetically coupled, triplet, ground state.