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首页> 外文期刊>Chemistry: A European journal >Addition of a Phosphinidene Complex to C=N Bonds:P-Ylides,Azaphosphiridines,and 1,3-Dipolsr Cycloadditions
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Addition of a Phosphinidene Complex to C=N Bonds:P-Ylides,Azaphosphiridines,and 1,3-Dipolsr Cycloadditions

机译：将膦亚基络合物加至C = N键：P-叶立德，氮杂吡啶和1,3-Dipolsr环加成

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摘要

The terminal phosphinidene complex PhPW(CO)_5 adds to the imine bond of PhHC=N-Ph to give 3-membered ring azaphosphiridines,which undergo ring-expansion with an additional imine to yield a set of four isomeric fivemembered ring diazaphospholanes.Treatment with the diimines PhHC=N-(CH_2)_n-N=CHPh (n=2,3,4) results instead-in all three cases-in only a single isomer of the (CH_2)_n bridged diazaphospholane.For n=2 or 3,this aminal group is easily hydrolyzed to arrord new 6- and 7-membred ring heterocycles.No intermediate azaphosphiridine complex is observed during the addition reaction to the diimines.B3LYP/6-31G~* calculations on an unsubstituted,uncomplexed system suggest that the initially formed P,N-ylide of the H_2C=N-(CH)_2-N=CH_2 diimine both kinetically and thermodynamically favors an intramolecular 1,3-dipoalr cycoladdition over an imine insertion into the CPN ring of an intermediate azaphosphiridine.Single-crystal X-ray structures for the (CH_2)_2-bridged azaphospholane complex and the HCl adduct of the 7-membered hydrolysis product are presented.
机译：末端次膦亚基配合物PhPW（CO）_5加到PhHC = N-Ph的亚胺键上，得到3元环氮杂膦啶，然后再与其他亚胺进行扩环，生成一组四个同分异构的五元环二氮杂膦环。在所有这三种情况下，仅在（CH_2）_n桥二氮磷戊烷的单一异构体中，二亚胺PhHC = N-（CH_2）_n-N = CHPh（n = 2,3,4）的结果.n = 2或3，该氨基基团很容易水解为新的6和7元环杂环。在与二亚胺的加成反应中没有观察到中间体氮杂磷杂环丁烷配合物。B3LYP/ 6-31G〜*在未取代，未配合的系统上的计算表明最初形成的H_2C = N-（CH）_2-N = CH_2二亚胺的P，N-内酯在动力学和热力学上均优于分子中的1,3-二足环乙酰胺加成反应，而不是将亚胺插入中间氮杂磷吡啶的CPN环中。 （CH_2）_2桥连的氮杂膦烷配合物的X射线晶体结构给出了7元水解产物的HCl加合物。

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