Synthesis of the 2,4,5-tri-tert-butyl-1,3-diphospholide anion by phosphinidene elimination from 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene on treatment with the amide Li[NPh(SiMe3)]
Synthesis of the 2,4,5-tri-tert-butyl-1,3-diphospholide anion by phosphinidene elimination from 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene on treatment with the amide Li[NPh(SiMe3)]
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DOI：
10.1002/chem.200601626
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Nyulaszi, Laszlo
中科院分区：
文献类型：
--
作者：
Clendenning, Scott B.;Hitchcock, Peter B.;Nyulaszi, Laszlo
氨基化锂Li[NPh]的处理（SiMe 3）]与2，4，6-三叔丁基-1，3，5-三磷杂苯，P（3）C（3）tBu（3）在1：2的比例得到等摩尔量的五元2，4，5-三叔丁基-1，3-二磷酰阴离子的锂盐Lip（2）C（3）tBu（3）（分离为其N，N，N '，N'-四甲基乙二胺（TMEDA）加合物）和三环化合物6-[苯基]-N-甲基-N，N，N'，N'-四甲基乙二胺（TMEDA）加合物（三甲基甲硅烷基）氨基]-3，5，7-三叔丁基-1，2，4，β 6-四磷酸-clo [3.2.0.0（2.7）]庚-3-烯。这两种化合物的结构特征已通过单晶X射线衍射研究。在B3 LYP/6-311+G** 水平上对该反应的机理进行了理论分析。该反应涉及到一个迄今未观察到的氨基亚膦，它是通过从三磷杂苯中提取一个磷原子而形成的。通过溶剂THF进一步稳定的中间体氨基亚膦显示出与先前的理论预测一致的增强的稳定性，然后与第二分子的三磷杂苯反应。
Treatment of the lithium amide Li[NPh(SiMe3)] with 2,4,6-tritet-t-butyl-1,3,5-triphosphabenzene, P(3)C(3)tBu(3), in a 1:2 ratio afforded equimolar amounts of the lithium salt of the five-membered 2,4,5-tri-tert-butyl-1,3-diphospholide anion, Lip(2)C(3)tBu(3) (isolated as its N,N,N',N'-tetramethylethylenediamine (TMEDA) adduct), and the tricyclic compound 6-[phenyl(trimethNIlsilvl)amino]-3,5,7-tri-tert- butyl-1,2,4,6-tetraphosphatricy-clo[3.2.0.0(2.7)]hept-3-ene. Both compounds have been structurally characterised by single-crystal X-ray diffraction studies. The mechanism of this remarkable reaction has been elucidated by theoretical methods at the B3LYP/6-311+G** level of theory. The reaction involves a hitherto unobserved aminophosphinidene, which was formed by abstraction of a phosphorus atom from triphosphabenzene. The intermediate aminophosphinidene, which is further stabilised by the solvent THF, shows, in agreement with previous theoretical predictions, enhanced stability and reacts then with a second molecule of triphosphabenzene.