The Chemistry of Inter-element Unsaturated Linkage

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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.