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

Published inOrganometallics, vol. 23, no. 23, p. 5410-5418
Publication date2004
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.

Citation (ISO format)
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. doi: 10.1021/om049559o
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