期刊
ORGANOMETALLICS
卷 30, 期 8, 页码 2377-2384出版社
AMER CHEMICAL SOC
DOI: 10.1021/om200116q
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资金
- Deutsche Forschungsgemeinschaft
- Fonds der Chemischen Industrie
- FONDECYT [1100286]
- Alexander von Humboldt-Stiftung
The chelate bis-imine nacnacH-CN (1) and its bis-phosphinimine analogue P-nacnacH-CN (2) are shown to have similar reactivities with HB(C6F5)(2). In a 1:1 stoichiometry simple Lewis acid/Lewis base adducts are observed: HB(C6F5)(2) just adds to the nitrile functionality to yield compounds 3 and 6, respectively. With two molar equivalents of HB(C6F5)(2), both systems 1 and 2 react at 70 degrees C with reduction of the nitrile group to an imine that is in both reactions found to be coordinated to a second equivalent of the HB(C6F5)(2) Lewis acid. The remaining B(C6F5)(2) unit becomes part of a six-membered heterocycle, where it is found to be coordinated to the pair of (C-NAr) (4) or (P-NPh) (7) units. Heating of the nacnacHw-CN/HB-(C6F5)(2) adduct 3 results in a disproportionation reaction yielding a mixture of the heterocycle (4) and the borane-free starting material 1. In marked contrast, the thermolysis of the P-nacnacH-CN/HB-(C6F5)(2) adduct (6) yields a new product (8), generated via an intramolecular -Ph2P=NPh vs -CH=NH exchange at the boron center and a formal Umpolung of a hydridic to a protic hydrogen atom. The compounds 3, 4, 6, 7, and 8 were characterized spectroscopically and by X-ray diffraction.
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