Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/34641
DC FieldValueLanguage
dc.contributor.authorCheng, R.J.en_US
dc.contributor.author陳如珍zh_TW
dc.contributor.authorChen, P.Y.en_US
dc.contributor.authorLovell, T.en_US
dc.contributor.authorLiu, T.Q.en_US
dc.contributor.authorNoodleman, L.en_US
dc.contributor.authorCase, D.A.en_US
dc.date2003zh_TW
dc.date.accessioned2014-06-06T07:48:05Z-
dc.date.available2014-06-06T07:48:05Z-
dc.identifier.issn0002-7863zh_TW
dc.identifier.urihttp://hdl.handle.net/11455/34641-
dc.description.abstractBonding interactions between the iron and the porphyrin macrocycle of five- and six-coordinate high-spin iron(III)-porphyrin complexes are analyzed within the framework of approximate density functional theory with the use of the quantitative energy decomposition scheme in combination with removal of the vacant pi* orbitals of the porphyrin from the valence space. Although the relative extent of the iron-porphyrin interactions can be evaluated qualitatively through the spin population and orbital contribution analyses, the bond strengths corresponding to different symmetry representations can be only approximated quantitatively by the orbital interaction energies. In contrast to previous suggestions, there are only limited Fe --> P pi* back-bonding interactions in high-spin iron(III)-porphyrin complexes. It is the symmetry-allowed bonding interaction between d(z)(2) and a(2u) orbitals that is responsible for the positive pi spin densities at the meso-carbons of five-coordinate iron(Ill)-porphyrin complexes. Both five- and six-coordinate complexes show significant P --> Fe pi donation, which is further enhanced by the movement of the metal toward the in-plane position for six-coordinate complexes. These bonding characteristics correlate very well with the NMR data reported experimentally. The extraordinary bonding interaction between d(z)(2) and a(2u) orbitals in five-coordinate iron(III)-porphyrin complexes offers a novel symmetry-controlled mechanism for spin transfer between the axial ligand sigma system and the porphyrin a system and may be critical to the electron transfer pathways mediated by hemoproteins.en_US
dc.language.isoen_USzh_TW
dc.relationJournal of the American Chemical Societyen_US
dc.relation.ispartofseriesJournal of the American Chemical Society, Volume 125, Issue 22, Page(s) 6774-6783.en_US
dc.relation.urihttp://dx.doi.org/10.1021/ja021344nen_US
dc.subjectnuclear-magnetic-resonanceen_US
dc.subjecttransition-state methoden_US
dc.subjectligand-fielden_US
dc.subjectstrengthen_US
dc.subjects = 3/2en_US
dc.subjectiron(iii) porphyrinsen_US
dc.subjectintermediate-spinen_US
dc.subjectmagnetochemical seriesen_US
dc.subjectferric porphyrinsen_US
dc.subjectiron porphyrinsen_US
dc.subjectvalent ironen_US
dc.titleSymmetry and bonding in metalloporphyrins. A modern implementation for the bonding analyses of five- and six-coordinate high-spin iron(III)-porphyrin complexes through density functional calculation and NMR spectroscopyen_US
dc.typeJournal Articlezh_TW
dc.identifier.doi10.1021/ja021344nzh_TW
item.languageiso639-1en_US-
item.openairetypeJournal Article-
item.cerifentitytypePublications-
item.grantfulltextnone-
item.fulltextno fulltext-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
Appears in Collections:化學系所
Show simple item record
 

Google ScholarTM

Check

Altmetric

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.