Aggregation of Donor Base Stabilized 2-Thienyllithium in a Single Crystal and in Solution: Distances from X-ray Diffraction and the Nuclear Overhauser Effect.
Various 2-thienyllithium derivatives were investigated in the solid state by X-ray diffraction and in solution by 2D NMR experiments. The determined structures of [(EtO)Li(CHS)] (1), [(THF)Li(CHS)] (2), [(DME)Li(CHS)] (3), [(TMEDA)Li(CHS)] (4), and [(PMDETA)Li(CHS)] (5) (DME = 1,2-dimethoxyethane, T...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 2; pp. 1344 - 1352 |
|---|---|
| Autores principales: | , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
1/18/2012
|
| 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=70786152&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 70786152 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: 1/18/2012 vid: 134 iid: 2 pid: 997 pub: American Chemical Society artinfo: ui: 70786152 10.1021/ja210382c ppf: 1344 ppct: 8 formats: tig: atl: Aggregation of Donor Base Stabilized 2-Thienyllithium in a Single Crystal and in Solution: Distances from X-ray Diffraction and the Nuclear Overhauser Effect. aug: au: Granitzka, Markus Pöppler, Ann-Christin Schwarze, Eike K. Stern, Daniel Schulz, Thomas John, Michael Herbst-Irmer, Regine Pandey, Sushil K. Stalke, Dietmar affil: Institut für Anorganische Chemie der Universität Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany Department of Chemistry, University of Jammu, Jammu-180 006, India su: Optical diffraction X-rays Overhauser effect (Nuclear physics) Spectrum analysis Nitrogen Thiophenes Deuterium sug: subj: Optical diffraction X-rays Overhauser effect (Nuclear physics) Spectrum analysis Nitrogen Thiophenes Deuterium ab: Various 2-thienyllithium derivatives were investigated in the solid state by X-ray diffraction and in solution by 2D NMR experiments. The determined structures of [(EtO)Li(CHS)] (1), [(THF)Li(CHS)] (2), [(DME)Li(CHS)] (3), [(TMEDA)Li(CHS)] (4), and [(PMDETA)Li(CHS)] (5) (DME = 1,2-dimethoxyethane, TMEDA = N,N,N',N'-tetramethylethylene-1,2-diamine, and PMDETA = N,N,N',N?,N?-pentamethyldiethylenetriamine) were solved in nondonating toluene and provide firm ground for diffusion-ordered NMR spectroscopy as well as heteronuclear Overhauser enhancement NMR spectroscopy. The distance relation of nuclear Overhauser effects with a factor of r is employed to gain further insight into the aggregation degree of 1-5 in solution. Comparison of the slope provided by the linear region of the buildup curves and of the Σr calculated distances from the crystal structures offers a handle to judge the structure retention versus conversion in solution. The structures of 3-5 are maintained in toluene solution. The data of 2, however, indicate a partial dissociation or a rapid exchange between the vertices of a tetrameric core and free THF molecules. Auxiliary exchange spectroscopy investigations showed that the signals of the nitrogen donor base containing compounds 4 and 5 exchange with the signals of nonlithiatedthiophene. This is explained by exchange of the deuterium by a hydrogen atom via lithiation of toluene molecules. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
|---|