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

1,6配位过磷阴离子（12-P-6）通常不稳定且难以分离。为了稳定阴离子，两种等效的双齿马丁配体（六氟癸醇）与三氯化磷原位反应生成4个配位磷阴离子（10-P-4）。共轭醛和1,2-二酮与阴离子（10-P-4）反应形成diols - alder型1,4-环加成，合成6个配位过磷酸阴离子（12-P-6）。用邻苯二酚作为1,2-二酮时，阴离子（12-P-6）被分离稳定，并用x射线分析确定了结构。一般来说，阴离子（12-P-6）水解得到5个含乙醛基团的配位磷烷（10-P-5），这些醛被表征为2,4-二硝基苯腙。本文报道了5种不同配位价碳（10-C-5）的合成及其x射线结构分析。2006年，我们尝试合成了6个配位价碳（12-C-6）。由于制备12-C-6的思路新颖独特，人们进行了多次尝试。最后，合成了末端1,3个碳为噻吩骨架的烯类化合物，并将两个硫原子甲基化，得到6个配位碳。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Riverside， California， usa的C. Reed教授小组开发。3 .混合五芳锑化合物的合成、晶体和溶液结构、配体交换和配体偶联反应在2007年发表全文。这些实验相当复杂，包含了高价五配位化合物的各个方面，并且在几年前就完成了。通过对整个实验结果的分析，认为该反应是通过两个顶配体进行的，这被称为“记忆效应”。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