PH-Functional Phosphines with 1,1'-Biphenyl-2,2'-bis(methylene) and 1,1'-Binaphthyl-2,2'-bis(methylene) Backbones.
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.
Bitterer
Frank
F
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.
Herd
Oliver
O
Kühnel
Michael
M
Stelzer
Othmar
O
Weferling
Norbert
N
Sheldrick
William S.
WS
Hahn
Jutta
J
Nagel
Sabine
S
Rösch
Notker
N