The Geometry of Coordinated Molecular Nitrogen. The Structure of Co(H)(N2)(P(C6H5)3)3
The Geometry of Coordinated Molecular Nitrogen. The Structure of Co(H)(N2)(P(C6H5)3)3
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配位分子氮的几何形状。
DOI：
10.1021/ja01033a049
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发表时间：
1969
影响因子：
15
通讯作者：
J. Ibers
中科院分区：
文献类型：
--
作者：
B. Davis;N. C. Payne;J. Ibers
(12)WR Roth，Chemia，20，229（1966）. (13)我们已经表明，在98 ℃（2%v/v庚烷溶液）加热75分钟时，反式异构体不会形成顺式-S，9-二氢茚（例如，通过两次1，5-氢迁移）。(14)对Dreiding模型的检查清楚地表明，这个过程只需要一个小的结构重组。Doering在他对科普重排的优美研究中证明了这个因素的重要性：W. von E. Doering和W. R. Roth，Tetrahedron，19，715（1963）. (15)1，3位移可以发生在构型反转时：J。A。贝尔森和G. L.纳尔逊，J. Am.化学会，89，5503（1967）。Israel等人也提出了这一方法，但涉及异氰酸酯中间体的替代机理也是可能的：M. Israel、LC Jones和E. J. Modest，Tetrahedron Lett.，4811（1968年）。(16)我们谨慎地使用这个术语，因为在活化的络合物中没有对称元素。(17)M. J. S. Dewar，Tetrahedron Suppl. 8，75（1967）。
(12) WR Roth, Chemia, 20, 229 (1966).(13) We have shown that cis-S, 9-dihydroindene is not formed from the trans isomer (eg, via two 1, 5-hydrogen migrations) to a significant extent upon heating at 98 (2% v/v in heptane) for 75 min.(14) Inspection of Dreiding models clearly shows that only a small structural reorganization is required for this process. The importance of this factor has been demonstrated by Doering in his elegant studies of the Cope rearrangement: W. von E. Doering and W. R. Roth, Tetrahedron, 19, 715 (1963).(15) A 1, 3 shift can occur with inversion of configuration: J. A. Berson and G. L. Nelson, J. Am. Chem. Soc., 89, 5503 (1967). This process has also been suggested by Israel, et at., but an alternate mechanism involving an isocyanate intermediate is also possible: M. Israel, LC Jones, and E. J. Modest, Tetrahedron Lett., 4811 (1968).(16) We use this term advisedly since there is no element of sym-metry in the activated complex.(17) M. J. S. Dewar, Tetrahedron Suppl., 8, 75 (1967).