PH-Functional Phosphines with 1,1'-Biphenyl-2,2'-bis(methylene) and 1,1'-Binaphthyl-2,2'-bis(methylene) Backbones
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- 作者：Frank Bitterer ; Oliver Herd ; Michael Kü ; hnel ; Othmar Stelzer ; Norbert Weferling ; William S. Sheldrick ; Jutta Hahn ; Sabine Nagel ; and Notker Rö ; sch
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：December 14, 1998
- 年：1998
- 卷：37
- 期：25
- 页码：6408 - 6417
- 全文大小：306K
- 年卷期：v.37,no.25(December 14, 1998)
- ISSN：1520-510X
文摘
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 PH3 or in a protected-group synthesis using P(SiMe3)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 thetwo CH2 and naphthyl substituents in the 13C{1H} NMR spectra. The X-ray crystal structure of 1·0.5C6H5CH3shows an intracyclic C-P-C angle of 99.5(2)
, the interplanar angle of the phosphepine ring system being 67.6(5).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 theconformations of 1, 3, and 14 are presented. The ability of these phosphines to form mononuclear and polynuclearcomplexes with transition-metal centers is discussed. Compound 14 exhibits a large variety of low-energyconformations, and some of them seem to be capable of forming mononuclear transition-metal complexes.
, the interplanar angle of the phosphepine ring system being 67.6(5).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 theconformations of 1, 3, and 14 are presented. The ability of these phosphines to form mononuclear and polynuclearcomplexes with transition-metal centers is discussed. Compound 14 exhibits a large variety of low-energyconformations, and some of them seem to be capable of forming mononuclear transition-metal complexes.