REACTIONS OF ALKYL AND HYDRIDE DERIVATIVES OF PERMETHYLSCANDOCENE AND PERMETHYLZIRCONOCENE WITH NITRILES AND AMINES - CATALYTIC-HYDROGENATION OF TERT-BUTYL CYANIDE WITH PERMETHYLSCANDOCENE HYDRIDE
REACTIONS OF ALKYL AND HYDRIDE DERIVATIVES OF PERMETHYLSCANDOCENE AND PERMETHYLZIRCONOCENE WITH NITRILES AND AMINES - CATALYTIC-HYDROGENATION OF TERT-BUTYL CYANIDE WITH PERMETHYLSCANDOCENE HYDRIDE
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DOI：
10.1021/om00134a009
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发表时间：
1986-03-01
期刊：
影响因子：
2.8
通讯作者：
WOLCZANSKI, PT
中科院分区：
文献类型：
--
作者：
BERCAW, JE;DAVIES, DL;WOLCZANSKI, PT
H，Me）和相应的胺，分别消除氢或甲烷。Cp* 2ScNHCH 2CMe 3将催化将Me 3CCN还原为Me 3CCH 2NH 2;然而，通过将腈插入钪-酰胺键中以形成Cp* 2ScNC（CMe 3）NHCH 2CMe 3而终止，其NC键在这些条件下不被氢化。标记实验表明，氢可以通过酰胺的Sc-N键可逆地加成，这一步骤被认为在催化反应中起着至关重要的作用。
H, Me) and the corresponding amine, with resultant elimination ofhydrogen or methane, respectively. Cp* 2ScNHCH2CMe3 will catalytically hydrogenate (4 atm of H2) Me3CCNto Me3CCH2NH2; however, termination occurs by insertion of the nitrile into the scandium-amide bond to form Cp* 2ScNC (CMe3) NHCH2CMe3, the NC bond of which is not hydrogenated under these conditions. Labeling experiments show that hydrogen can add reversibly across the Sc-N bond of the amide, and this step is believed to play a crucial role in the catalytic reaction.