Several Rh(I), Ir(III), and Pt(II) complexes of the chiral P,S-bidentate ligand 2 have been prepared and characterized. Detailed two-dimensional NMR studies show that (i) the boat-type chelate ring and the stereogenic sulfur center can invert rapidly at ambient temperature and (ii) the sulfur donor may dissociate, essentially destroying the chiral pocket. The solid-state structure of [Pt(eta(3)-C3H5)(2)]PF6 (3) has been determined and the sulfur substituent shown to have an axial orientation. The six-membered chelate ring takes up a boatlike conformation. As shown by an X-ray diffraction study for 3, and via incoherent inelastic neutron scattering (IINS) measurements for the Pd analog, 4, the OH group is remote from the metal atom.
|Titolo:||NMR studies of chiral P,S-chelate platinum, rhodium, and iridium complexes and the X-ray structure of a palladium(II) allyl derivative|
ALBINATI, ALBERTO (Primo)
|Parole Chiave:||nuclear-magnetic-resonance; asymmetric catalytic allylation; metal-complexes; ferrocenyl ligands; crystal-structures; alkylation; chemistry; mechanism; PD; hydroboration|
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||18-feb-1997|
|Digital Object Identifier (DOI):||10.1021/om960823q|
|Appare nelle tipologie:||01 - Articolo su periodico|