trans-W(Cmesityl)(dmpe)H: Revealing a Highly Polar W-H Bond and H-Mobility in Liquid and Solid State.
The isotopomeric complexes trans-W(Cmesityl)[(C(H,D))PCHCHP(C(H,D))](H,D) 1-4 were prepared. 2 (W(C)(dmpe)D) was used to study the Deuterium Quadrupole Coupling Constant (DQCC) and the ionicity of the W-D bond (DQCC = 34.1 kHz; ionicity 85%). 1 (W(C)(dmpe)H) shows several dynamic exchange processes...
| Publicado en: | Journal of the American Chemical Society Vol. 129; no. 22; pp. 7195 - 7206 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
6/6/2007
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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=25501699&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 25501699 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: 6/6/2007 vid: 129 iid: 22 pid: 997 pub: American Chemical Society artinfo: ui: 25501699 10.1021/ja069140k ppf: 7195 ppct: 11 formats: tig: atl: trans-W(Cmesityl)(dmpe)H: Revealing a Highly Polar W-H Bond and H-Mobility in Liquid and Solid State. aug: au: Fenglou Zou Furno, Franck Fox, Thomas Schmalle, Helmut W. Berke, Heinz Eckert, Jurgen Chowdhury, Zema Burger, Peter affil: Anorganisch-chemisches Institut, Universität Zurich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland LANSCE-LC, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 Materials Research Laboratory, University of California, Santa Barbara, California 93106 NIST Center for Neutron Research, Bldg 235, Gaithersburg, Maryland 20899 su: Deuterium Optical diffraction Isomerization Neutrons Scattering (Physics) sug: subj: Deuterium Optical diffraction Isomerization Neutrons Scattering (Physics) ab: The isotopomeric complexes trans-W(Cmesityl)[(C(H,D))PCHCHP(C(H,D))](H,D) 1-4 were prepared. 2 (W(C)(dmpe)D) was used to study the Deuterium Quadrupole Coupling Constant (DQCC) and the ionicity of the W-D bond (DQCC = 34.1 kHz; ionicity 85%). 1 (W(C)(dmpe)H) shows several dynamic exchange processes in solution, such as H/H, H/ortho-Me, and H/H exchanges observed by NMR in combination with deuterium labeling studies and double label crossover experiments. Except for the H/H, these reactions comprise elementary steps, which also appear along the isomerization pathway of 1 into (2,3,5-trimethylphenylcarbyne)(dmpe)WH (5) at 60 °C. 5 was characterized by an X-ray diffraction study. In the solid state only an H/Me exchange process prevails appearing at higher temperatures, which was identified by NMR and by Quasielastic Neutron Scattering. The latter also provided an activation barrier of 5 kcal/mol and a "jump width" for the moving H nucleus in agreement with the H⋯Me distance of the X-ray diffraction study of 1. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2007 holdings: @attributes: islocal: N |
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