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DFT study of the geometry and energy order of the low singlet and triplet states of [d4-η5-CpMo(CO)2X] 16-electron complexes (X = halogen, CN, H, and CH3)

Show simple item record Hasanayn F. Markarian M.-Z. Al-Rifai R.
dc.contributor.editor 2004 2017-10-03T15:45:36Z 2017-10-03T15:45:36Z 2004
dc.identifier 10.1021/ic0354973
dc.identifier.issn 00201669
dc.description.abstract DFT methods have been used to investigate the dependence of the geometry and energy order of the low energy states of [d4-η 5-CpMo(CO)2X] 16-electron complexes on X (X = halogen, CN, H and CH3). The calculations use a double-ζ plus polarization valence basis set on all atoms and utilize relativistic ECPs on Mo and the heavier halogens. In every case two singlet and two triplet electronic states have been considered and minimized at the B3LYP level. For X = Cl, additional calculations were carried out at the BPW91, CCSD(T), and CASSCF levels. In the Cs point group, the singlet states are from the (1a′) 2(1a″)2 and (1a′)2(2a′) 2 configurations of the valence d4 electrons of the metal, and are denoted 1A′-a and 1A′-b, respectively. The triplet species are for the lowest 3A″ and 3A′ states from the (1a′)2(2a′) 1(1a″)1 and (1a″)2(1a′) 1(2a′)1 d4 configurations. For all substituents, the geometry of both the singlet and triplet states is found to distort substantially from the uniform 3-leg piano-stool structural motif, a behavior that can be related to Jahn-Teller effects. When X is a halogen or a methyl, 1A′-b is predicted to be lower than 1A′-a, while the reverse order of these two singlet states is calculated for X = H and CN. For all substituents 3A′ is substantially higher than 3A″. In turn, the energy of 3A″ is calculated to be comparable to the lower singlet state of each complex. Attempts are made to rationalize some of these results using qualitative MO theory.
dc.format.extent Pages: (3691-3696)
dc.language English
dc.publisher WASHINGTON
dc.relation.ispartof Publication Name: Inorganic Chemistry; Publication Year: 2004; Volume: 43; no. 12; Pages: (3691-3696);
dc.source Scopus
dc.title DFT study of the geometry and energy order of the low singlet and triplet states of [d4-η5-CpMo(CO)2X] 16-electron complexes (X = halogen, CN, H, and CH3)
dc.type Article
dc.contributor.affiliation Hasanayn, F., Department of Chemistry, American University of Beirut, Beirut, Lebanon
dc.contributor.affiliation Markarian, M.-Z., Department of Chemistry, American University of Beirut, Beirut, Lebanon
dc.contributor.affiliation Al-Rifai, R., Department of Chemistry, American University of Beirut, Beirut, Lebanon
dc.contributor.authorAddress Hasanayn, F.; Department of Chemistry, American University of Beirut, Beirut, Lebanon; email:
dc.contributor.authorCorporate University: American University of Beirut; Faculty: Faculty of Arts and Sciences; Department: Chemistry;
dc.contributor.authorDepartment Chemistry
dc.contributor.faculty Faculty of Arts and Sciences
dc.contributor.authorInitials Hasanayn, F
dc.contributor.authorInitials Markarian, MZ
dc.contributor.authorInitials Al-Rifai, R
dc.contributor.authorReprintAddress Hasanayn, F (reprint author), Amer Univ Beirut, Dept Chem, Beirut, Lebanon.
dc.contributor.authorUniversity American University of Beirut
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dc.description.citedCount 5
dc.description.citedTotWOSCount 5
dc.description.citedWOSCount 5
dc.format.extentCount 6
dc.identifier.coden INOCA
dc.identifier.scopusID 2942578970
dc.publisher.address 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
dc.relation.ispartOfISOAbbr Inorg. Chem.
dc.relation.ispartOfIssue 12
dc.relation.ispartofPubTitle Inorganic Chemistry
dc.relation.ispartofPubTitleAbbr Inorg. Chem.
dc.relation.ispartOfVolume 43
dc.source.ID WOS:000221989000020
dc.type.publication Journal
dc.subject.otherIndex halogen
dc.subject.otherIndex metal derivative
dc.subject.otherIndex article
dc.subject.otherIndex atomic particle
dc.subject.otherIndex calculation
dc.subject.otherIndex chemical structure
dc.subject.otherIndex density functional theory
dc.subject.otherIndex electron
dc.subject.otherIndex energy
dc.subject.otherIndex geometry
dc.subject.otherIndex mathematical analysis
dc.subject.otherIndex polarization
dc.subject.otherIndex structure analysis
dc.subject.otherKeywordPlus D6 ML5 COMPLEXES
dc.subject.otherKeywordPlus M = MO
dc.subject.otherKeywordPlus CONFIGURATION-INTERACTION
dc.subject.otherKeywordPlus OXIDATIVE ADDITION
dc.subject.otherKeywordPlus REACTIVITY
dc.subject.otherKeywordPlus CARBONYL
dc.subject.otherKeywordPlus LIGAND
dc.subject.otherKeywordPlus H-2
dc.subject.otherKeywordPlus THERMODYNAMICS
dc.subject.otherKeywordPlus PHOTOCHEMISTRY
dc.subject.otherWOS Chemistry, Inorganic and Nuclear

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