Preparation and Properties of RhI and IrI Ethylene Complexes Containing the ChiralP,N-Chelate Ligand (4S)-2-[2-(Diphenylphosphanyl)phenyl]-4-isopropyl-1,3-oxazoline

Abstract

The synthesis and characterization of the chiral complexes [MCl(η 2 -C 2 H 4 )(PN)] [M = Rh (1), Ir (2)] and [IrCl(η 2 -C 2 H 4 ) 2 (PN)] (3) {PN = (4S)-2-[2-(diphenylphosphanyl)phenyl]-4-isopropyl-1,3-oxazoline}, including the X-ray crystal structure of 2, are reported. The solution behavior has been studied by NMR spectroscopy. For the rhodium com-

New chiral oxazoline based-rhodium(I) catalysts: Synthesis, characterisation, heterogeneisation and applications

“…IR spectra (film) show the characteristic m C@N band at 1643-1653 cm À1 , in good agreement with values reported in the literature for structurally close bis(oxazoline) complexes [35,36]. 13 C NMR spectra of the complexes 4-6 gave a signal at 168-172 ppm corresponding to the C@N of the oxazoline ring.…”

Diastereoselective Synthesis of Chiral Octahedral Iridium(III) Phosphano–Oxazoline Complexes

“…A notable family of chiral P,N ligands are phosphano–oxazolines (PN*), which have been successfully applied to a variety of metal-catalyzed asymmetric reactions . In particular, some years ago, we reported the preparation and characterization of Ir(I)/PN i Pr compounds , (PN i Pr = (4 S )-2-[2-(diphenylphosphanyl)phenyl]-4-isopropyl-4,5-dihydrooxazole) and tested the catalytic activity of some of them in asymmetric Michael additions …”

“…1 H NMR (400.16 MHz, CD 2 Cl 2 , room temperature): δ 8.6−6.6 (34H, Ar); 3.82 (d, J = 8.8 Hz, 1H, H 52 ); 3.62 m, 2.04 td, J = 15.4, 5.5 Hz (2H, H 11 , H 12 ); 3.55 m, 2.52 psp, J = 7.3 MeMeCH); −0.60 (d, J = 6.6, 3H, MeMeCH); −19.03 (dpt, J = 21.2, 9.7 Hz, 1H, Ir-H). 31 P{ 1 H} NMR (161.96, CD 2 Cl 2 , room temperature): δ −1.04, −12.36 (AB part of an ABX system, J(AB) = 355 4. Hz, J = 20.1, 17 4.…”

“…31 P{ 1 H} NMR (161.96, CD 2 Cl 2 , room temperature): δ −1.04, −12.36 (AB part of an ABX system, J(AB) = 355 4. Hz, J = 20.1, 17 4. Hz, 2P, P 3 , P 1 ); −38.33 (pt, P 2 ).…”