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Article: Structural and electron density studies on a chromium(IV)-oxo complex [CrIV(O)(TMP)]

TitleStructural and electron density studies on a chromium(IV)-oxo complex [CrIV(O)(TMP)]
Authors
KeywordsCr-ooxo bond
Crystal structure
Electron density
Issue Date1999
PublisherThe Chemical Society. The Journal's web site is located at http://www.sinica.edu.tw/~ccswww/jccs.htm
Citation
Journal Of The Chinese Chemical Society, 1999, v. 46 n. 3, p. 487-493 How to Cite?
AbstractThe electron density distribution of a chromium(IV)-oxo complex, [CrIV(O)(TMP)] (TMP = 5,10,15,20-tetrakis-p-methoxyphenyl porphyrin), is investigated by molecular orbital calculation. The molecular and crystal structure of the compound is studied by x-ray diffraction. It belongs to the space group I 2, Z = 2, a = 14.979(4) Å, b = 9.752(3), c = 15.605(3) Å, β = 100.97(2)°, V = 2238(1) Å3, Mo Kα radiation λ = 0.7107 Å, R = 4.9%, Rw = 3.5% for 3575 observed reflections. Cr is five-coordinated in a square pyramidal fashion with the Cr atom located 0.42 Å toward the oxo-ligand. Deformation density maps are derived from the single point molecular orbital calculation on the basis of HF and DFT(density functional theory) calculations. The accumulation of deformation density along the C-H, C-C, C-N and C-O bonds in the porphyrin ligand is well represented. The asphericity in electron density around the Cr ion is clearly demonstrated. Natural bond orbital analysis (NBO) reveals that the Cr-Ooxo is actually a triple-bond character (σ2π4) and the four N of pyrrole serves as a σ-donor to Cr. The Cr-Npyrrole bond is essentially a dative bond. d-Orbital populations of Cr derived from both calculations are in good agreement with each other. Planar dπ-orbital is the most populated, which is in accord with the prediction from crystal field theory. Detail bond characterization of the Cr-L, multiple bond is discussed.
Persistent Identifierhttp://hdl.handle.net/10722/69103
ISSN
2015 Impact Factor: 0.879
2015 SCImago Journal Rankings: 0.290
References

 

DC FieldValueLanguage
dc.contributor.authorLin, HMen_HK
dc.contributor.authorSheu, HSen_HK
dc.contributor.authorWang, CCen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorWang, Yen_HK
dc.date.accessioned2010-09-06T06:10:35Z-
dc.date.available2010-09-06T06:10:35Z-
dc.date.issued1999en_HK
dc.identifier.citationJournal Of The Chinese Chemical Society, 1999, v. 46 n. 3, p. 487-493en_HK
dc.identifier.issn0009-4536en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69103-
dc.description.abstractThe electron density distribution of a chromium(IV)-oxo complex, [CrIV(O)(TMP)] (TMP = 5,10,15,20-tetrakis-p-methoxyphenyl porphyrin), is investigated by molecular orbital calculation. The molecular and crystal structure of the compound is studied by x-ray diffraction. It belongs to the space group I 2, Z = 2, a = 14.979(4) Å, b = 9.752(3), c = 15.605(3) Å, β = 100.97(2)°, V = 2238(1) Å3, Mo Kα radiation λ = 0.7107 Å, R = 4.9%, Rw = 3.5% for 3575 observed reflections. Cr is five-coordinated in a square pyramidal fashion with the Cr atom located 0.42 Å toward the oxo-ligand. Deformation density maps are derived from the single point molecular orbital calculation on the basis of HF and DFT(density functional theory) calculations. The accumulation of deformation density along the C-H, C-C, C-N and C-O bonds in the porphyrin ligand is well represented. The asphericity in electron density around the Cr ion is clearly demonstrated. Natural bond orbital analysis (NBO) reveals that the Cr-Ooxo is actually a triple-bond character (σ2π4) and the four N of pyrrole serves as a σ-donor to Cr. The Cr-Npyrrole bond is essentially a dative bond. d-Orbital populations of Cr derived from both calculations are in good agreement with each other. Planar dπ-orbital is the most populated, which is in accord with the prediction from crystal field theory. Detail bond characterization of the Cr-L, multiple bond is discussed.en_HK
dc.languageengen_HK
dc.publisherThe Chemical Society. The Journal's web site is located at http://www.sinica.edu.tw/~ccswww/jccs.htmen_HK
dc.relation.ispartofJournal of the Chinese Chemical Societyen_HK
dc.subjectCr-ooxo bonden_HK
dc.subjectCrystal structureen_HK
dc.subjectElectron densityen_HK
dc.titleStructural and electron density studies on a chromium(IV)-oxo complex [CrIV(O)(TMP)]en_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0009-4536&volume=46&spage=487&epage=493&date=1999&atitle=Structural+and+electron+density+studies+on+a+chromium(IV)-oxo+complex+[CrIV)(O)(TMP)]en_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.scopuseid_2-s2.0-14644422815en_HK
dc.identifier.hkuros53198en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-14644422815&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume46en_HK
dc.identifier.issue3en_HK
dc.identifier.spage487en_HK
dc.identifier.epage493en_HK
dc.publisher.placeTaiwanen_HK
dc.identifier.scopusauthoridLin, HM=36336985700en_HK
dc.identifier.scopusauthoridSheu, HS=35594761100en_HK
dc.identifier.scopusauthoridWang, CC=35202304900en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridWang, Y=36072665800en_HK

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