title: PH-Functional Phosphines with 1,1'-Biphenyl-2,2'-bis(methylene) and 1,1'-Binaphthyl-2,2'-bis(methylene) Backbones.
abstract: The first PH-functional phosphines (1, 3, and 5) containing the 1,1'-binaphthyl-2,2'-bis(methylene) or 1,1'-biphenyl-2,2'-bis(methylene) backbone have been obtained by two-phase phosphination of 2,2'-bis(halomethyl)-1,1'-binaphthyls with PH(3) or in a protected-group synthesis using P(SiMe(3))(3) as the starting material. The 4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]phosphepine (1) is configurationally stable, as indicated by the inequivalence of the two CH(2) and naphthyl substituents in the (13)C{(1)H} NMR spectra. The X-ray crystal structure of 1.0.5C(6)H(5)CH(3) shows an intracyclic C-P-C angle of 99.5(2) degrees, the interplanar angle of the phosphepine ring system being 67.6(5) degrees. The borane adduct 7 of the secondary phosphine 1 has been employed for the syntheses of atropisomeric mono- and bidentate ligands (8-14) with the bulky 1,1'-binaphthyl moieties. Results of force field calculations on the conformations of 1, 3, and 14 are presented. The ability of these phosphines to form mononuclear and polynuclear complexes with transition-metal centers is discussed. Compound 14 exhibits a large variety of low-energy conformations, and some of them seem to be capable of forming mononuclear transition-metal complexes.
authors.affiliation: Fachbereich 9, Anorganische Chemie, Bergische Universität-GH Wuppertal, D-42097 Wuppertal, Germany, Clariant GmbH, Werk Knapsack, D-50351 Hürth-Knapsack, Germany, Lehrstuhl für Analytische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany, and Lehrstuhl für Theoretische Chemie, Technische Universität München, D-85747 Garching, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Bitterer
authors.forename: Oliver
authors.initials: O
authors.lastname: Herd
authors.forename: Michael
authors.initials: M
authors.lastname: Kühnel
authors.forename: Othmar
authors.initials: O
authors.lastname: Stelzer
authors.forename: Norbert
authors.initials: N
authors.lastname: Weferling
authors.forename: William S.
authors.initials: WS
authors.lastname: Sheldrick
authors.forename: Jutta
authors.initials: J
authors.lastname: Hahn
authors.forename: Sabine
authors.initials: S
authors.lastname: Nagel
authors.forename: Notker
authors.initials: N
authors.lastname: Rösch