| pubmed-article:16117536 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:16117536 | lifeskim:mentions | umls-concept:C0439855 | lld:lifeskim |
| pubmed-article:16117536 | lifeskim:mentions | umls-concept:C0013850 | lld:lifeskim |
| pubmed-article:16117536 | lifeskim:mentions | umls-concept:C0678594 | lld:lifeskim |
| pubmed-article:16117536 | pubmed:issue | 34 | lld:pubmed |
| pubmed-article:16117536 | pubmed:dateCreated | 2005-8-24 | lld:pubmed |
| pubmed-article:16117536 | pubmed:abstractText | The geometric and electronic structure of the untethered heme-peroxo-copper model complex [(F(8)TPP)Fe(III)-(O(2)(2)(-))-Cu(II)(TMPA)](ClO(4)) (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 Cu...Fe distance of approximately 3.72 A. Spin-unrestricted DFT calculations for the S(T) = 2 spin state were performed on [(P)Fe(III)-(O(2)(2)(-))-Cu(II)(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 mu-eta(1):eta(2) coordination mode. The calculated Cu...Fe distance is approximately 0.3 A longer than that observed experimentally. Reoptimization of [(P)Fe(III)-(O(2)(2)(-))-Cu(II)(TMPA)](+) with a 3.7 A Cu...Fe constrained distance results in a similar energy and structure that retains the overall mu-eta(1):eta(2)-peroxo coordination mode. The primary bonding interaction between the copper and the peroxide involves electron donation into the half-occupied Cu d(z)2 orbital from the peroxide pi(sigma) orbital. In the case of the Fe(III)-peroxide eta(2) bond, the two major components arise from the donor interactions of the peroxide pi*(sigma) and pi*(v) orbitals with the Fe d(xz) and d(xy) orbitals, which give rise to sigma and delta bonds, respectively. The pi*(sigma) interaction with both the half-occupied d(z)2 orbital on the copper (eta(1)) and the d(xz) orbital on the iron (eta(2)), provides an effective superexchange pathway for strong antiferromagnetic coupling between the metal centers. | lld:pubmed |
| pubmed-article:16117536 | pubmed:grant | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:grant | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:grant | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:language | eng | lld:pubmed |
| pubmed-article:16117536 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:citationSubset | IM | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:16117536 | pubmed:status | MEDLINE | lld:pubmed |
| pubmed-article:16117536 | pubmed:month | Aug | lld:pubmed |
| pubmed-article:16117536 | pubmed:issn | 0002-7863 | lld:pubmed |
| pubmed-article:16117536 | pubmed:author | pubmed-author:SolomonEdward... | lld:pubmed |
| pubmed-article:16117536 | pubmed:author | pubmed-author:HedmanBrittB | lld:pubmed |
| pubmed-article:16117536 | pubmed:author | pubmed-author:HodgsonKeith... | lld:pubmed |
| pubmed-article:16117536 | pubmed:author | pubmed-author:KarlinKenneth... | lld:pubmed |
| pubmed-article:16117536 | pubmed:author | pubmed-author:ChufánEduardo... | lld:pubmed |
| pubmed-article:16117536 | pubmed:author | pubmed-author:SarangiRitimu... | lld:pubmed |
| pubmed-article:16117536 | pubmed:author | pubmed-author:Del RíoDiegoD | lld:pubmed |
| pubmed-article:16117536 | pubmed:issnType | Print | lld:pubmed |
| pubmed-article:16117536 | pubmed:day | 31 | lld:pubmed |
| pubmed-article:16117536 | pubmed:volume | 127 | lld:pubmed |
| pubmed-article:16117536 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:16117536 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:16117536 | pubmed:pagination | 11969-78 | lld:pubmed |
| pubmed-article:16117536 | pubmed:dateRevised | 2007-11-14 | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:meshHeading | pubmed-meshheading:16117536... | lld:pubmed |
| pubmed-article:16117536 | pubmed:year | 2005 | lld:pubmed |
| pubmed-article:16117536 | pubmed:articleTitle | Geometric and electronic structure of the heme-peroxo-copper complex [(F8TPP)FeIII-(O22-)-CuII(TMPA)](ClO4). | lld:pubmed |
| pubmed-article:16117536 | pubmed:affiliation | Department of Chemistry, Stanford University, Stanford, California 94305, USA. | lld:pubmed |
| pubmed-article:16117536 | pubmed:publicationType | Journal Article | lld:pubmed |
| pubmed-article:16117536 | pubmed:publicationType | Research Support, U.S. Gov't, P.H.S. | lld:pubmed |
| pubmed-article:16117536 | pubmed:publicationType | Research Support, U.S. Gov't, Non-P.H.S. | lld:pubmed |
| pubmed-article:16117536 | pubmed:publicationType | Research Support, Non-U.S. Gov't | lld:pubmed |
| pubmed-article:16117536 | pubmed:publicationType | Research Support, N.I.H., Extramural | lld:pubmed |
| http://linkedlifedata.com/r... | pubmed:referesTo | pubmed-article:16117536 | lld:pubmed |
