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Title

Toward an Understanding of the Anion Effect in CpRu-Based Diels-Alder Catalysts via PGSE-NMR Measurements

Authors
Anil Kumar, P.G.
Pregosin, P.S.
Published in Organometallics. 2004, vol. 23, no. 23, p. 5410-5418
Abstract The rate dependence of the [Ru(η5-C5H5)(BIPHOP-F)(acetone)][Y]-catalyzed Diels-Alder reaction of cyclopentadiene with methacrolein on the anion, Y, is shown to be due to selective ion pairing. Pulsed gradient spin-echo (PGSE) diffusion measurements on the model Cp and indenyl complexes [Ru(η5-C5H5)(CH2CH==CN)(BIPHOP-F)][Y], Y = BF4 and BArF, and [Ru(η5-C9H7)(CH2CH==CN)(BIPHOP-F)][Y], Y = BF4 and BArF, respectively, combined with 1H-19F HOESY NMR data can be used to understand how the ion pairing for the BF4 anion differs relative to that of the BArF anion. Solid-state structures for [Ru(η5-C5H5)(CH2CH==CN)(BIPHOP-F)][BF4] and [Ru(η5-C5H5)(CH2CH==CN)(BIPHOP-F)][BArF] are reported and support the NMR solution data. The model carbonyl complexes [Ru(η5-C5H5)(BIPHOP-F)(CO)][Y], 8 (Y = BF4, SbF6, and BArF) have been synthesized. The IR CO stretching frequencies for 8 showed little variation with anion, thereby proving that the anions do not affect the Lewis acidity of the salts.
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ANIL KUMAR, P.G. et al. Toward an Understanding of the Anion Effect in CpRu-Based Diels-Alder Catalysts via PGSE-NMR Measurements. In: Organometallics, 2004, vol. 23, n° 23, p. 5410-5418. https://archive-ouverte.unige.ch/unige:6944

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Deposited on : 2010-06-18

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