title: Coordination chemistry of phosphanyl amino acids: solid state and solution structures of neutral and cationic rhodium complexes.
abstract: Copper phosphide or arsenide complexes, [Cu(EPh(2))(neo)] (E = P, As, neo = 2,9-dimethyl-1,10-phenanthroline; trivial name: neocuprine) react selectively with the N-protected brominated serine derivatives, 2-(S)-(alkoxycarbonylamino)-3-bromomethylpropionates ((ROCO)SerBr, : R = PhCH(2), : tBu, : Me) to give the corresponding phosphanylated or arsanylated amino acids, (ROCO)SerPhos (: Phos = PPh(2)) and (Z)SerArs (Ars = AsPh(2), Z = PhCH(2)OCO). The dipeptide (Z)AlaSerPhos was likewise prepared. The phosphanes , and the arsane reacted cleanly with [Rh(2)(micro-Cl)(2)(cod)(2)] to give the rhodium(I) complexes [RhCl(cod)((Z)SerPhos)] , [RhCl(cod)((Boc)SerPhos)] (Boc = tBuOCO), [RhCl(cod)((Z)AlaSerPhos)] , and [RhCl(cod)((Z)SerArs)] which were characterized by X-ray diffraction studies. A common structural feature is an intramolecular (N)H[dot dot dot]Cl(Rh)-hydrogen bridge which according to NMR investigations remains intact in solution. The abstraction of chloride from the coordination sphere of Rh(I) in or has a profound structural impact. While in and , the ligands bind in a monodentate fashion, via the phosphorus atom only, they serve as bidentate ligands via the phosphorus centre and the peptidic C=O group in [Rh(cod)(kappa(2)-(Z)SerPhos)]PF(6) and [Rh(cod)(kappa(2)-(Z)AlaSerPhos)]PF(6). This causes also the amino acid residue structures to change from alpha-helix type in and to a beta-sheet type in both. Addition of chloride to and fully re-establishes the structures of both. The complexes [RhCl(cod)((Z)SerPhos)] and [RhCl(cod)((Boc)SerPhos)] show good activities in homogeneously catalyzed hydrogenations of olefins while the dipeptide complex is less active. Phosphane addition to greatly diminishes the catalytic activity. The cationic complex [Rh(cod)(kappa(2)-(Z)AlaSerPhos)]PF(6) shows low activity which, however, is greatly increased by addition of one equivalent of phosphane.
authors.affiliation: Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Hönggerberg, HCI H131, CH-8093, Zürich, Switzerland.
authors.forename: Christian
authors.initials: C
authors.lastname: Meyer
authors.forename: Markus
authors.initials: M
authors.lastname: Scherer
authors.forename: Hartmut
authors.initials: H
authors.lastname: Schönberg
authors.forename: Heinz
authors.initials: H
authors.lastname: Rüegger
authors.forename: Sandra
authors.initials: S
authors.lastname: Loss
authors.forename: Volker
authors.initials: V
authors.lastname: Gramlich
authors.forename: Hansjörg
authors.initials: H
authors.lastname: Grützmacher
mesh_terms: D000596:Amino Acids / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines; D012238:Rhodium / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D000596:Amino Acids; D009942:Organometallic Compounds; D010720:Phosphines; D012238:Rhodium; C044646:phosphine