The Chemistry of Inter-element Unsaturated Linkage

1. 以2,4-二叔丁基-6-甲基苯基为保护基团的二硫代磷烷脱硫反应得到相应的二硫代磷烷，该二硫代磷烷缓慢三聚生成三硫代三膦烷并分离得到。1-三（三烷基硅基）环三硅烯进行光异构反应得到相应的双环[1.1.0]四硅烷，并以反加成方式加成醇。作为副产物，分离得到了螺戊二烯衍生物，并对其进行了表征。构成3元2-π电子芳族体系的环三格烯离子与庞大的亲核试剂反应生成环三格烯，不对称地取代在饱和的锗原子上。双键周围的构象取决于取代基的电子和空间效应。以醋酸或1,1,1 -三氟乙醇为质子源，研究了含马丁配体的五配位1,2-草硅烷类化合物的热反应。1,2- oxasiletanides被认为是一种反应中间体，根据3位的体积和质子源的酸度，可以用于Peterson反应和homo-Brook重排。利用2,6-二[二（三甲基硅基）甲基]-4-[三（三甲基硅基）甲基]苯基，制备了一种新型的双键化合物，并对其进行了表征。考虑到取代基的电子和空间效应，通过理论计算，提出了一种真正的硅三键化合物二苯乙烯是稳定的。类似地，含锗、锡和铅的三键也被计算出来，硅萘和硅苯也被计算出来。

1. Desulfurization reaction of a dithioxophosphorane bearing the 2,4-di-t-butyl-6-methylphenyl group as protecting moiety gave the corresponding dithioxophosphine, which slowly trimerized to trithiatriphosphinane and isolated.2. Photoisomerization of a 1-tris (trialkylsilyl) cyclotrisilene proceeded to give the corresponding bicyclo [1.1.0] tetrasilane, and the addition of an alcohol occurred in the anti-addition mode. Furthermore, as byproduct, the spiropentasiladiene derivative was isolated and characterized.3. A cyclotrigermenium ion, constituting the 3-membered 2-π electron aromatic system, reacted with a bulky nucleophile to give a cyclotrigermene, unsymmetrically substituted at the saturated germanium atom. It was found that the conformation around the double bond depends on the electronic and steric effects of the substituent.4. Thermal reaction of penta-coordinated 1,2-oxasiletanides bearing the Martin ligand were studied in the presence of acetic acid or 1, 1, 1-trifluoroethanol as proton source. 1,2-Oxasiletanides is considered to be a reaction intermediate, which serves for the Peterson reaction and the homo-Brook rearrangement depending upon the bulkiness at the 3-position as well as the acidity of the proton source.5. Utilizing the 2,6-bis [bis (trimethylsilyl) methyl)-4-[tris (trimethylsilyl) methyl] phenyl group, a novel stibabismuthene as a double bond compound between two different group 15 elements, was prepared and characterized.6. Taking the electronic and steric effect of substituents into account, a real triple bond compounds of silicon, disilyne, has been proposed to be stabilized, by theoretical calculation. Similarly triple bonds containing germanium, tin, and lead ware calculated as well as silanaphthalene and silabenzene.