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

Anil Kumar, P.G.; Pregosin, P.S.; Vallet, Martial; Bernardinelli, Gérald Hugues; Jazzar, Rodolphe; Viton, Florian; Kundig, Ernst Peter

doi:10.1021/om049559o

Scientific article

English

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

ContributorsAnil Kumar, P.G.; Pregosin, P.S.; Vallet, Martial; Bernardinelli, Gérald Hugues; Jazzar, Rodolphe; Viton, Florian; Kundig, Ernst Peter

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.

Affiliation

Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

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

Article

Identifiers

PID : unige:6944
DOI : 10.1021/om049559o

ISSN of the journal0276-7333

593views

0downloads

Creation06/18/2010 8:54:34 AM

First validation06/18/2010 8:54:34 AM

Update time03/14/2023 3:30:23 PM

Status update03/14/2023 3:30:23 PM

Last indexation02/12/2024 6:23:45 PM

Archive ouverte UNIGE

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

Technical informations