Innovation of 6 Coordinate Hypervalent Compounds Bearing Carbon and Phosphorus as Central Atoms

1，6配位过磷酰胺阴离子(12-P-6)通常不稳定，难以分离。为了稳定阴离子，双齿马丁配体的两个等价物(六氟辛醇)与三氯化磷反应，原位生成4配位的磷酰胺阴离子(10-P-4)。用共轭醛和1，2-二酮与阴离子(10-P-4)反应，形成Diels-Alder型1，4-环加成反应，合成了6配位过磷酰胺阴离子(12-P-6)。当苯二酮作为1，2-二酮时，阴离子(12-P-6)分离稳定，结构经X-射线分析确定。总而言之，阴离子(12-P-6)被水解得到5个含有乙醛基团的协式膦(10-P-5)，这些醛被表征为它们的2，4-二硝基苯肼。2.报道了5种配位高价碳物种(10-C-5)的合成和结构测定，作为20…财政年度的全文更多的05。2006年，我们挑战合成了6个配位的高价碳物种(12-C-6)。由于制备12-C-6物种的新的和独特的想法，人们尝试了几次。最后，合成了在1，3-碳末端带有硫杂菲骨架的联烯化合物，并将两个硫原子甲基化得到6个配位的碳物种。对于甲基化，只有最强的甲基化试剂，即碳硼烷试剂，才能成功。该试剂由美国加利福尼亚州Riverside的C.Reed Group教授开发。3，混合五芳基锑化合物的合成、晶体和溶液结构、配体交换和配体偶联反应是2007年的一篇全文报道。这些实验相当复杂，包含了高价五配位化合物的各种方面，并已在几年前完成。通过对整个实验结果的分析，认为该反应是通过两个根尖配体进行的，称为“记忆效应”。较少

1,6 Coordinate perphosphoranide anion (12-P-6) are usually unstable and difficult to be isolated. In order to stabilize the anion, two equivalents of the bidentate Martin ligand (hexafluorocumyl alcohol) were reacted with phosphorus trichloride to generate 4 coordinate phosphoranide anion (10-P-4) in situ. Conjugate aldehydes and 1,2-diketones were reacted with the anion (10-P-4) to effect Diels-Alder type 1,4-cycloadditon to synthesize 6 coordinate perphosphoranide anions (12-P-6). The anion (12-P-6) was isolated stable and the structure was determined by X-ray analysis when phenanhrenequinone was used as a 1,2-diketone. Gnerally, the anions (12-P-6) were hydrolyzed to give 5 cordinate phosphoranes (10-P-5) bearing ethylene aldehyde group and the aldehydes were characterixed as their 2,4-dinitrophenylhydrazones.2,Syntheses and structure determination by X-ray analysis of a variety of 5 coordinate hypervalent carbon species (10-C-5) were reported as full papers in the fiscal year of 20 … More 05. In 2006, we challenged to synthesize 6 coordinate hypervalent carbon species (12-C-6). Because of the new and unique idea to prepare 12-C-6 species, several attempts were tried. Finally, an allene compound which bears thioxanthene skeleton at the terminal 1,3-carbons was prepared and the two sulfur atoms were methylated to yield the 6 coordinate carbon species. For the methylation, only the strongest methylation reagent, i.e., carborane reagent, could lead to success. The reagent was developed by Professor C. Reed group of Riverside, California, USA.3,Syntheses, crystal and solution structures, ligand exchange and ligand coupling reactions of mixed pentaarylantimony compounds were reported as a full paper in 2007. The experiments were quite complicated and contained a variety of aspects of hypervalent pentacoordinate compounds and had been completed several years before. By analyzing the total experimental results, it was concluded that the reaction proceeded through the two apical ligands which was termed as "memory effect". Less