Geometric and Electronic Structure of the Heme-Peroxo-Copper Complex [(FTPP)Fe-(O)-Cu"(TMPA)](CIO).
The geometric and electronic structure of the untethered heme–peroxo–copper model complex [(FTPP)Fe–(O)–Cu(TMPA)](ClO) (1) has been investigated using Cu and Fe K-edge EXAFS spectroscopy and density functional theory calculations in order to describe its geometric and electronic structure. The Fe an...
| Published in: | Journal of the American Chemical Society Vol. 127; no. 34; pp. 11969 - 11979 |
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| Main Authors: | , , , , , , |
| Format: | Article |
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American Chemical Society
8/31/2005
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=18186835&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 18186835 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 8/31/2005 vid: 127 iid: 34 pid: 997 pub: American Chemical Society artinfo: ui: 18186835 10.1021/ja043374r ppf: 11969 ppct: 10 formats: tig: atl: Geometric and Electronic Structure of the Heme-Peroxo-Copper Complex [(FTPP)Fe-(O)-Cu"(TMPA)](CIO). aug: au: del RíO, Diego Sarangi, Ritimukta Chufän, Eduardo E. Karlin, Kenneth D. Hedman, Britt Hodgson, Keith O. Solomon, Edward I. affil: Department of Chemistry, Stanford University. Department of Chemistry, Johns Hopkins University. Stanford Synchrotron Radiation Laboratory. su: Electronic structure Extended X-ray absorption fine structure Spectrum analysis Density functionals Copper Particles (Nuclear physics) sug: subj: Electronic structure Extended X-ray absorption fine structure Spectrum analysis Density functionals Copper Particles (Nuclear physics) ab: The geometric and electronic structure of the untethered heme–peroxo–copper model complex [(FTPP)Fe–(O)–Cu(TMPA)](ClO) (1) has been investigated using Cu and Fe K-edge EXAFS spectroscopy and density functional theory calculations in order to describe its geometric and electronic structure. The Fe and Cu K-edge EXAFS data were fit with a CuߪFe distance of ∼3.72 Å. Spin-unrestricted DFT calculations for the S = 2 spin state were performed on [(P)Fe–(O)–Cu(TMPA)] as a model of 1. The peroxo unit is bound end-on to the copper, and side-on to the high-spin iron, for an overall μ-η¹; η² coordination mode. The calculated CuߪFe distance is ∼0.3 Å longer than that observed experimentally. Fleoptimization of [(P)Fe–(O)–Cu(TMPA)] with a 3.7 Å CuߪFe constrained distance results in a similar energy and structure that retains the overall μ-η¹η²-peroxo coordination mode. The primary bonding interaction between the copper and the peroxide involves electron donation into the half-occupied Cu d orbital from the peroxide π* orbital. In the case of the Fe––peroxide η² bond, the two major components arise from the donor interactions of the peroxide π* and π* orbitals with the Fe d and d orbitals, which give rise to σ and δ bonds, respectively. The π* interaction with both the half-occupied d orbital on the copper (η¹) and the d orbital on the iron (η²), provides an effective superexchange pathway for strong antiferromagnetic coupling between the metal centers. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2005 holdings: @attributes: islocal: N |
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