The C--H Activation of Methane by Laser-Ablated Zirconium Atoms: CH=ZrH, the Simplest Carbene Hydride Complex, Agostic Bonding, and (CH)ZrH.
Reaction of laser-ablated Zr with CH (CH, CD, and CHD) in excess neon during condensation at 5 K forms CH == ZrH, the simplest alkylidene hydride complex, which is identified by infrared absorptions at 1581.0, 1546.2, 757.0, and 634.5 cm. Density functional theory electronic structure calculations u...
| Publicado en: | Journal of the American Chemical Society Vol. 127; no. 1; pp. 465 - 474 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
1/12/2005
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| 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=15998396&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 15998396 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: 1/12/2005 vid: 127 iid: 1 pid: 997 pub: American Chemical Society artinfo: ui: 15998396 10.1021/ja0451259 ppf: 465 ppct: 9 formats: tig: atl: The C--H Activation of Methane by Laser-Ablated Zirconium Atoms: CH=ZrH, the Simplest Carbene Hydride Complex, Agostic Bonding, and (CH)ZrH. aug: au: Han-Gook Cho Xuefeng Wang Andrews, Lester affil: Department of Chemistry, University of Virginia, P.O. Box 400319, Charlottesville, Virginia 22904-4319. su: Density functionals Electronic structure Functional analysis Noble gases Nonmetals sug: subj: Density functionals Electronic structure Functional analysis Noble gases Nonmetals ab: Reaction of laser-ablated Zr with CH (CH, CD, and CHD) in excess neon during condensation at 5 K forms CH == ZrH, the simplest alkylidene hydride complex, which is identified by infrared absorptions at 1581.0, 1546.2, 757.0, and 634.5 cm. Density functional theory electronic structure calculations using a large basis set with polarization functions predict a C symmetry structure with agostic C--H- - -Zr bonding and distance of 2.300 Å. Identification of the agostic CH == ZrH methylidene complex is confirmed by an excellent match of calculated and observed isotopic frequencies particularly for the four unique CHD==ZrHD isotopic modifications. The analogous reactions in excess argon give two persistent photoreversibie matrix configurations for CH==ZrH. Finally, methane activation by, CH==ZrH gives the new (CH)ZrH molecule. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2005 holdings: @attributes: islocal: N |
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