Selective anion effects in chiral complexes of iridium via diffusion and HOESY data: relevance to catalysisElectronic supplementary information (ESI) available: spectroscopic data for 6b. See http://www.rsc.org/suppdata/cc/b1/b110066c/

Abstract

1H and 19F Pulsed Gradient Spin Echo (PGSE) diffusion data, together with 1H, 19F-HOESY results are shown to distinguish between different types of anion/cation interactions in chiral dihydrido-P,N-complexes of Ir(III); in CD2Cl2 the diffusion coefficients, D, for the BArF and the Ir-cation suggest ion-pairing whereas the D-values for PF6-reveal independent motion; the PF6- approaches the cation via a specific pathway; the combined PGSE/HOESY approach offers a unique opportunity for exploring anion effects in organometallic/catalytic chemistry.

Ligand Design for Catalytic Asymmetric Reduction

“…A chiral carbene-oxazoline ligand L5 is also useful for this purpose. 59 The mechanism of this reaction is to be elucidated by experimental [60][61][62][63] and theoretical 64,65 studies. Chiral titanocene catalysts also show high enantioselectivity for hydrogenation of simple olefins.…”

Deuterium exchange promoted by iridium complexes formed in situ

“…3 Alternatively, the complex is generated in the presence of the substrate, and the mixture exposed to deuterium without removal of the silver salts. 1 This method is not recommended, as the remaining silver salts are prone to be reduced on exposure to deuterium, as evidenced by the formation of a silver mirror on the interior of the flask.…”

Low Temperature 1H‐, 19F‐, and 31P‐PGSE Diffusion Measurements. Applications to Cationic Alcohol Complexes

“…For salts of transition metals, the PGSE diffusion methodology, frequently in combination with NOE data, offers a unique structural approach to this problem. By means of these methods, the relative anion-dependent activity of the Ir phosphinooxazoline (PHOX) complexes 1 in the catalytic hydrogenation of olefins in CH 2 Cl 2 can be explained [6] [19] [20].When no …”