Silylidyne, HSi≡MoH and HSi≡WH, and Silyl Metal Hydride, SiH—CrH, Products in Silane Reactions.
Laser-ablated group 6 metal atoms react with silane to form inserted SiH-MH hydride intermediates, which are identified from M-H and Si-H stretching modes. Following two successive α-H-transfers, the HSiMH (M = Mo, W) silylidyne molecules are produced. These silicon-metal triple-bonded species are...
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 21; pp. 6766 - 6774 |
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| Autores principales: | , |
| Formato: | Artículo |
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American Chemical Society
5/28/2008
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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=32574859&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 32574859 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: 5/28/2008 vid: 130 iid: 21 pid: 997 pub: American Chemical Society artinfo: ui: 32574859 10.1021/ja710810x ppf: 6766 ppct: 8 formats: tig: atl: Silylidyne, HSi≡MoH and HSi≡WH, and Silyl Metal Hydride, SiH—CrH, Products in Silane Reactions. aug: au: Xuefeng Wang Andrews, Lester affil: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319 su: Atoms Silane Hydrides Carbynes Density functionals Methane Molecules Silicon Deuterium sug: subj: Atoms Silane Hydrides Carbynes Density functionals Methane Molecules Silicon Deuterium ab: Laser-ablated group 6 metal atoms react with silane to form inserted SiH-MH hydride intermediates, which are identified from M-H and Si-H stretching modes. Following two successive α-H-transfers, the HSiMH (M = Mo, W) silylidyne molecules are produced. These silicon-metal triple-bonded species are identified as major products from the strong M-H stretching modes through deuterium substitution and comparison with frequencies and intensities from density functional calculations and from the analogous methylidynes. The silylidynes have calculated C structures and longer Si-H bonds than silane, but the C methylidyne analogues have shorter C-H bonds than methane. The SiMo and SiW bonds are polarized differently and have slightly lower effective bond orders than their carbon analogues. In addition, calculations for the group 6 silylidene molecules reveal C structures with no evidence of agostic distortion, in contrast to the corresponding methylidene molecules. 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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