Synthesis of Cyclic Vinylidene Complexes and Azavinylidene Complexes by Formal [4+2] Cyclization Reactions.
Synthesis of Cyclic Vinylidene Complexes and Azavinylidene Complexes by Formal [4+2] Cyclization Reactions.
复制标题
DOI：
10.1002/chem.201504618
复制
发表时间：
2016-04
期刊：
影响因子：
--
通讯作者：
Jinxiang Chen;Zi-Ao Huang;Zhengyu Lu;Hong Zhang;H. Xia
中科院分区：
文献类型：
--
作者：
Jinxiang Chen;Zi-Ao Huang;Zhengyu Lu;Hong Zhang;H. Xia
二乙烯基-丁烯基碳炔配合物[OsHCl 2（OsCC（PPh 3）=CHEt）（PPh 3）2] BF 4（1）与腈类RCN（R=2-环丙基-2-氧代丙基，3-氨基-2-氧代丁基）反应生成六元环亚乙烯基配合物3和氮杂亚乙烯基配合物4，即异锇吡啶鎓。在空气存在下，在CHCl 3中，在回流温度下用过量的2-甲酰基苄腈处理1，产生稠合的锇吡啶鎓 8，其首先氧化成三环异锇吡啶鎓衍生物7，然后氧化成含有稠合萘酮片段的异锇吡啶鎓 9。异锇吡啶鎓 9（具有亚乙烯基链段）向异锇吡啶鎓化合物10和11（具有氮杂亚乙烯基链段）的转化在卤化氢如HCl或HI的存在下实现。合成的配合物的分子结构通过X-射线研究证实。此外，通过密度泛函理论计算，研究了锇吡啶鎓的芳香稳定能和非核依赖化学位移值以及异锇吡啶鎓环中的应变。
Reactions of the hydrido-butenylcarbyne complex [OsHCl2(≡CC(PPh3)=CHEt)(PPh3)2]BF4 (1) with nitriles RC≡N (R=2-cyclopropyl-2-oxopropyl, 3-amino-2-oxobutyl) lead to six-membered cyclic vinylidene complexes 3 and azavinylidene complexes 4, that is, iso-osmapyridiniums. Treatment of 1 with excess 2-formylbenzonitrile at reflux temperature in CHCl3 in the presence of air produces a fused osmapyridinium 8, which is first oxidized to the tricyclic iso-osmapyridinium derivative 7, then to iso-osmapyridinium 9, which contains a fused naphthalenone fragment. The conversion of iso-osmapyridinium 9 (with a vinylidene segment) to the iso-osmapyridinium compounds 10 and 11 (with azavinylidene segments) was achieved in the presence of a hydrogen halide, such as HCl or HI. The molecular structures of the complexes synthesized were confirmed by X-ray studies. Moreover, the aromatic stabilization energy and nucleus-independent chemical-shift values of the osmapyridiniums and the strain in the iso-osmapyridinium rings were investigated by DFT calculations.