PhP(BH)Li: From Ditopicity to Dual Reactivity.
A multinuclear NMR study shows that the deprotonation of diphenyiphosphine-orane by n-BuLi in THF leads to a disolvated lithium phosphido-borane Ph2P(BH3)Li of which L1 is connected to the hydrides on the boron and two THF molecules rather than to the phosphorus. This entity behaves as both a phosph...
| Publicado en: | Journal of the American Chemical Society Vol. 133; no. 16; pp. 6472 - 6481 |
|---|---|
| Autores principales: | , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
4/27/2011
|
| 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=60439759&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 60439759 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: 4/27/2011 vid: 133 iid: 16 pid: 997 pub: American Chemical Society artinfo: ui: 60439759 10.1021/ja201760c ppf: 6472 ppct: 9 formats: tig: atl: PhP(BH)Li: From Ditopicity to Dual Reactivity. aug: au: Consiglio, Gabriella Barozzino Queval, Pierre Harrison-Marchand, Anne Mordini, Alessandro Lohier, Jean-Francois Delacroix, Olivier Gaumont, Annie-Claude Gérard, Hélëne Maddaluno, Jacques Oulyadit, Hassan affil: Laser Thermal Laboratory, Department of Mechanical Engineering, University of California, Berkeley, California 94720, United States Department of Bioengineering, University of California, Berkeley, California 94720, United States Department of Materials Science and Engineering, University of California, Berkeley, California 94720, United States Department of Bioengineering, University of Washington, Seattle, Washington 98185, United States su: Nuclear magnetic resonance Proton transfer reactions Boranes Density functionals Phosphorus sug: subj: Nuclear magnetic resonance Proton transfer reactions Boranes Density functionals Phosphorus ab: A multinuclear NMR study shows that the deprotonation of diphenyiphosphine-orane by n-BuLi in THF leads to a disolvated lithium phosphido-borane Ph2P(BH3)Li of which L1 is connected to the hydrides on the boron and two THF molecules rather than to the phosphorus. This entity behaves as both a phosphination and a reducing agent, depending on the kinetic or thermodynamic control imposed to the reaction medium. Density functional theory computations show that H2P(BH3)Li exhibits a ditopic character (the lithium cation can be in the vicinity ot the hydride or of the phosphorus). It explains its dual reactivity (H- or P-addition), both routes going through somewhat similar six- membered transition states with low activation barriers. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2011 holdings: @attributes: islocal: N |
|---|