ETA(3) AND ETA(6) BRIDGING CATIONS IN THE N,N,N',N'',N''-PENTAMETHYLDIETHYLENETRIAMINE-SOLVATED COMPLEXES OF BENZYLPOTASSIUM AND BENZYLRUBIDIUM - AN X-RAY, NMR, AND MO STUDY

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Details zur Publikation

Autorinnen und Autoren: Hoffmann D, Bauer W, Hampel F, van Eikema Hommes N, Schleyer P, Otto P, Pieper U, Stalke D, Wright D, Snaith R
Zeitschrift: Journal of the American Chemical Society
Verlag: American Chemical Society
Jahr der Veröffentlichung: 1994
Band: 116
Heftnummer: 2
Seitenbereich: 528-536
ISSN: 0002-7863


Abstract


The metalation of toluene (PhCH3) with a 1:1 mixture of n-BuLi/MO(t)Bu (M = K,Rb) at ambient temperature affords orange-red powders of benzylpotassium or benzylrubidium. On addition of N,N,N,N'',N''-pentamethyldiethylenetriamine (PMDTA) the precipitates dissolve to give burgundy-red solutions, from which needles of [PhCH2K.PMDTA.0.5PhCH3]n (1) or [PhCH2Rb.PMDTA]n (2) are obtained. X-ray analysis reveals that 1 incorporates half a molecule of toluene per asymmetric unit. In both 1 and 2, the eta3 and eta6 interaction of one M+ cation with two benzyl fragments gives rise to the formation of polymeric chains. The coordination sphere of the cations is completed by one chelating triamine ligand. MO calculations predict multihapto metal carbon interactions to become more important from Li to Cs and substantiate the solid-state results. Ab initio calculations on three different polymers suggest that the array present in the crystal structure is the most stable. The gated decoupled C-13 NMR spectrum of 1 in THF-d8 solution reveals a 1J(C-13,H-1) coupling constant for the benzylic carbon atom which may be interpreted in terms of a mainly planar configuration of the CH2- group in solution.



FAU-Autorinnen und Autoren / FAU-Herausgeberinnen und Herausgeber

Bauer, Walter apl. Prof. Dr.
Lehrstuhl für Organische Chemie II
Hampel, Frank Dr.
Lehrstuhl für Organische Chemie I
Schleyer, Paul Prof. Dr.
Naturwissenschaftliche Fakultät
van Eikema Hommes, Nico Dr.
Computer-Chemie-Centrum


Einrichtungen weiterer Autorinnen und Autoren

Georg-August-Universität Göttingen
Julius-Maximilians-Universität Würzburg
University of Cambridge


Zitierweisen

APA:
Hoffmann, D., Bauer, W., Hampel, F., van Eikema Hommes, N., Schleyer, P., Otto, P.,... Snaith, R. (1994). ETA(3) AND ETA(6) BRIDGING CATIONS IN THE N,N,N',N'',N''-PENTAMETHYLDIETHYLENETRIAMINE-SOLVATED COMPLEXES OF BENZYLPOTASSIUM AND BENZYLRUBIDIUM - AN X-RAY, NMR, AND MO STUDY. Journal of the American Chemical Society, 116(2), 528-536. https://dx.doi.org/10.1021/ja00081a013

MLA:
Hoffmann, Daniele, et al. "ETA(3) AND ETA(6) BRIDGING CATIONS IN THE N,N,N',N'',N''-PENTAMETHYLDIETHYLENETRIAMINE-SOLVATED COMPLEXES OF BENZYLPOTASSIUM AND BENZYLRUBIDIUM - AN X-RAY, NMR, AND MO STUDY." Journal of the American Chemical Society 116.2 (1994): 528-536.

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