title: (1)H and (19)F PGSE diffusion and HOESY NMR studies on cationic palladium (II) 1,3-diphenylallyl complexes in THF solution.
abstract: THF solutions of the cationic chiral 1,3-diphenylallyl bidentate phosphine complexes [Pd(eta(3)-PhCHCHCHPh)(Duphos)](CF(3)SO(3)), Duphos = 1,2-Bis-((2R,5R)-2,5-dimethylphospholano)benzene), 2, and [Pd(eta(3)-PhCHCHCHPh)(P,S)]BF(4), 4, P,S = [8-((o-(diphenylphosphino)benzyl) thiomethyl]-(7,7'-dimethyl)-exo-norborneol, have been studied via pulsed gradient spin-echo (PGSE) diffusion, (1)H, (19)F HOESY and a variety of other multi-dimensional NMR methods. On the basis of the (1)H, (19)F HOESY data, the anions show a preference for a specific structural position with respect to the eta(3)-PhCHCHCHPh allyl ligand, i.e. the anion does not move evenly around the periphery of the cation. THF is shown to promote significant ion pairing, although neither 2 nor 4 shows 100% ion pairing.
authors.affiliation: Laboratory of Inorganic Chemistry, ETHZ, HCI Hönggerberg, CH-8093 Zürich, Switzerland.
authors.forename: Ignacio
authors.initials: I
authors.lastname: Fernández
authors.forename: Paul S
authors.initials: PS
authors.lastname: Pregosin
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry* / Q000145:classification; D002412:Cations; D004058:Diffusion; D005461:Fluorine / Q000737:chemistry; D005663:Furans / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry* / Q000145:classification; D010165:Palladium / Q000737:chemistry* / Q000145:classification; D010720:Phosphines / Q000737:chemistry; D012996:Solutions / Q000737:chemistry
chemical_list: D000498:Allyl Compounds; D002412:Cations; D005663:Furans; D009942:Organometallic Compounds; D010720:Phosphines; D012996:Solutions; D005461:Fluorine; C018674:tetrahydrofuran; D010165:Palladium; D006859:Hydrogen