Bonding of Seven Carbonyl Groups to a Single Metal Atom: Theoretical Study of M(CO) (M = Ti, Zr, Hf; n = 7, 6, 5, 4).
The equilibrium geometries, thermochemistry, and vibrational frequencies of the homoleptic metal-carbonyls of the group 4 elements, M(CO) (M = Ti, Zr, Hf; n = 7, 6, 5, 4) were predicted using density functional theory. Analogous M(CO) structures were found for all three metals. The global minima for...
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 24; pp. 7756 - 7761 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
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American Chemical Society
6/18/2008
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=34106867&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 34106867 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: 6/18/2008 vid: 130 iid: 24 pid: 997 pub: American Chemical Society artinfo: ui: 34106867 10.1021/ja8003655 ppf: 7756 ppct: 5 formats: tig: atl: Bonding of Seven Carbonyl Groups to a Single Metal Atom: Theoretical Study of M(CO) (M = Ti, Zr, Hf; n = 7, 6, 5, 4). aug: au: Qiong Luo Qian-Shu Li Zhong Heng Yu Yaoming Xie King, R. Bruce Schaefer III, Henry F. affil: Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631 China School of Chemistry and Chemical Engineering, Central South University, Changsha, 410083 China, State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100080 China Institute of Chemical Physics, Beijing Institute of Technology, Beijing 100081, China Department of Chemistry and Center for Computational Chemistry, University of Georgia, Athens, Georgia 30602 su: Metals Thermochemistry Density functionals Functional analysis Atoms sug: subj: Metals Thermochemistry Density functionals Functional analysis Atoms ab: The equilibrium geometries, thermochemistry, and vibrational frequencies of the homoleptic metal-carbonyls of the group 4 elements, M(CO) (M = Ti, Zr, Hf; n = 7, 6, 5, 4) were predicted using density functional theory. Analogous M(CO) structures were found for all three metals. The global minima for the 1 8-electron M(CO)7 molecules are all singlet C capped octahedra. The global minima for the 16-electron M(CO) species are triplet M(CO) structures distorted from O symmetry to D symmetry. However, the corresponding singlet M(CO) structures lie within 5 kcal/mol of the triplet global minima. The global minima for M(CO) (n = 5, 4) are triplet structures derived from the D distorted octahedral structures of M(CO) by removal of one or two CO groups, respectively. Quintet D trigonal bipyramidal structures for M(CO) and singlet T tetrahedral structures for M(CO) are also found, as well as higher energy structures for M(CO) and M(CO) containing a unique CO group bonded to the metal atom through both M-C and M-O bonds. The dissociation energies M(CO) → M(CO) + CO are substantial, indicating no fundamental problem in bonding seven CO groups to a single metal atom. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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