Attempted Synthesis of 1-Aza-3λ3-phospha-1-allenide Complexes: Structure and Reactions of an Unusual Phosphanide Complex
Attempted Synthesis of 1-Aza-3λ3-phospha-1-allenide Complexes: Structure and Reactions of an Unusual Phosphanide Complex
复制标题
1-Aza-3λ3-phospha-1-allenide 配合物的尝试合成：不寻常的 Phosphanide 配合物的结构和反应
DOI：
10.1021/om070240o
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发表时间：
2007
期刊：
影响因子：
2.8
通讯作者：
R. Streubel
中科院分区：
文献类型：
--
作者：
Aysel Özbolat;G. V. Frantzius;E. Ionescu;S. Schneider;M. Nieger;and Peter G. Jones;R. Streubel
第一个N-锂化氰基膦配合物5a-c的合成是通过配合物1与tBuLi/12-冠-4、NaN（SiMe 3）2/15-冠-5或KOtBu/18-冠-6在低温下反应实现的。化合物5a-c被分离并通过NMR和IR光谱和元素分析充分表征。配合物5a的结构，如通过X-射线衍射研究所建立的，揭示了锂与氮和氧中心（冠醚单元的）配位。5a的这种几何形状最好描述为与膦酰亚胺络合物异构的膦化物络合物。在熔体中观察到5a的类膦化合物行为，通过经由LiCN消除和解络合形成环三膦4来证明。在溶液5a中，与碘甲烷（或三氟甲磺酸甲酯）像磷化物一样反应，从而产生P-甲基络合物8。
Synthesis of the first N-lithiated cyanophosphanide complexes 5a−c was achieved via reaction of complex 1 with tBuLi/12-crown-4, NaN(SiMe3)2/15-crown-5, or KOtBu/18-crown-6 at low temperature. Compounds 5a−c were isolated and fully characterized by NMR and IR spectroscopy and elemental analysis. The structure of complex 5a, as established by X-ray diffraction studies, revealed that the lithium is coordinated to nitrogen and the oxygen centers (of the crown ether unit). This geometry of 5a is best described as a phosphanide complex isomeric to a phosphinidenoid complex. A phosphinidenoid-like behavior of 5a was observed in the melt, evidenced by formation of cyclotriphosphane 4 via LiCN elimination and decomplexation. In solution 5a reacted with methyl iodide (or methyl triflate) like a phosphanide, thus leading to P-methyl complex 8.