- Direct Synthesis of Silylamine from N2and a Silane: Mediated by a Tridentate Phosphine Molybdenum Fragment
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A homogeneous system which is able to yield silylamine from N2and bis(silane) in one pot is reported. Mechanistically a {(triphosphine)molybdenum(I)} fragment, generated in situ, splits N2into the corresponding nitrido complex at room temperature. Then, functionalization of the molybdenum nitrido is achieved by double Si?H addition under mild reaction conditions. Moreover, the bis(silyl)amine product is decoordinated from the metal center.
- Liao, Qian,Cavaillé, Anthony,Saffon-Merceron, Nathalie,Mézailles, Nicolas
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- Stepwise Functionalization of N2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex
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Functionalization of nitrido complex [(PPhP2Cy)Mo(N)(I)] by a bis-silane in concentrated medium generates the hydrido-imido complex [(PPhP2Cy)Mo(H)(=NSiMe2CH2CH2SiMe2H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF6, OTf) results in a second N–Si bond formation and forms the bis-hydride amide complex [(PPhP2Cy)Mo(H)2(NSiMe2CH2CH2SiMe2)]+. An alternative synthesis relies on the abstraction of the iodide from the nitride complex [(PPhP2Cy)Mo(N)(I)] to generate the corresponding cationic complex [(PPhP2Cy)Mo(N)]+ followed by addition of the bis-silane. Addition of PMe3 to the [(PPhP2Cy)Mo(H)2(NSiMe2CH2CH2SiMe2)]+ complex liberates the silylamine and forms the Mo(II) cationic complex [(PPhP2Cy)Mo(H)(PMe3)]+. DFT calculations rationalizing the observed reactivity are presented.
- Bennaamane, Soukaina,Clot, Eric,Espada, Maria F.,Fustier-Boutignon, Marie,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie,Yagoub, Ikram
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- Multiple Bonds Between Main-Group Elements and Transition Metals, CXX. - Niobium and Tantalum Amide Complexes and New Cyclocarbodisilazanes
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The new niobium- and tantalum complexes 3a and 3b of formula (M = Nb, a; Ta, b) are accessible by the reaction of the oxychlorides MOCl3 with the lithium amide (2) in 30 and 19percent isolated yield, resp.The new silazanes cyclo2 (5) and cyclo-3 (6) are prepared from (CH3)2ClSiCH2CH2SiCl(CH3)2 and NH3.Their structures - ten- and fifteeen-membered rings - were determined by single-crystal structure analyses. Key Words: Niobium complexes / Tantalum complexes / Silylamides / Cyclocarbodisilazanes
- Herrmann, Wolfgang A.,Dyckhoff, Florian,Herdtweck, Eberhardt
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p. 2651 - 2656
(2007/10/02)
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- A Convenient Synthesis of Primary Amines by N-Alkylation of Cyclic Potassium Disilylamides
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Potassium 2,6-disilapiperidide, readily prepared from 2,2,6,6-tetramethyl-2,6-disilapiperidine and potassium hydride, can be smoothly N-alkylated with alkyl halides to give the corresponding primary amines after acid hydrolysis.Keywords- potassium 2,6-disilapiperidide; potassium hydride; primary amine; N-alkylation; metal amide
- Hosomi, Akira,Kohra, Shinya,Tominaga, Yoshinori,Inaba, Masahiro,Sakurai, Hideki
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p. 2342 - 2345
(2007/10/02)
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