Construction and Functions of Dynamic Complexes Composed of Transition Metal/Efetero-Element Systems

1.硅基和芳基(硅烯)配合物上1，2-和1，3-迁移反应的实验证据我们发展了无给电子体的硅基(硅烯)铁配合物Cp^*Fe(CO)(=Simes_2)SiMe_3(1)的热和光化学合成方法，并测定了它的X-射线晶体结构。在CO存在下，1在80℃下进行热反应，得到了二硅氧基配合物Cp^*Fe(CO)_2SiMeMesSiMe_2Mes(2a)及其异构体2b。2a或2b的光解反应定量地复制了1。这些结果为硅基(硅烯)络合物中非常简单的1，2-和1，3-基团迁移反应提供了最直接的证据。同样，我们发现，在(芳基硅钨配合物)上，硅基配体上的芳基在碱的存在下发生了1，2-迁移到配位的不饱和金属中心，得到了碱稳定的硅烯配合物。氢化硅烯钨配合物的合成、结构及反应活性：Cp^*(CO)_3WMe与空间受阻的三氢…的光反应更多的硅烷H_3SiC(SiMe_3)_3在密封管中形成氢化氢(氢化硅)络合物和硅基络合物。通过周期性地去除CO的辐照，将氢化硅烯络合物分离为单一产物。对氢化硅烯配合物η^5C5Me_4Et的晶体结构分析和核磁共振波谱分析表明，氢化硅烯配体间存在较强的相互作用，密度泛函理论计算也支持这一结果。氢化硅烯络合物与酮、烯酮、腈、环氧杂环己烷等多种极性分子顺利反应，得到新型加成产物。磷硅铁环丙烷与不同极性分子的反应：羰基(膦硅基)铁配合物在低温下通过CO解离得到磷硅铁环丙烷。磷硅铁环丙烷与几个具有极化不饱和键的有机分子如4-二甲氨基吡啶、苯甲醛、酮和烯酮反应，得到具有五元螯合环的插入产物。它还与具有极化单键E-H(E=O、S、N和P)的各种分子在室温下瞬间反应生成硅基(氢膦)铁配合物。较少

1. Experimental Evidences for 1,2-and 1,3-Migration Reactions on Silyl-and Aryl(silylene) Complexes We developed thermal as well as photochemical synthetic methods for a donor-free silyl(silylene)iron complex Cp^*Fe(CO)(=SiMes_2)SiMe_3 (1), and determined its X-ray crystal structure. Thermal reaction of 1 at 80℃ in the presence of CO gave a disilanyl complex Cp^*Fe(CO)_2SiMeMesSiMe_2Mes (2a) and its isomer 2b. Photolysis of either 2a or 2b reproduced 1 quantitatively. These results provide the most straightforward evidences for extremely facile 1,2- and 1,3-group migration reactions in silyl(silylene) complexes. Similarly, we found that, on an (arylsilyDtungsten complex, an aryl group on the silyl ligand underwent 1,2-migration to a coordinatively unsaturated metal center in the presence of base to give a base-stabilized silylene complex.2. Synthesis, Structures, and Reactivity of Hydrido(hydrosilylene)tungsten Complexes : Photoreaction of Cp^*(CO)_3WMe with sterically hindered trihydr … More osilane H_3SiC(SiMe_3)_3 in a sealed tube afforded a mixture of hydridoOiydrosilylene) complex and a silyl complex. The hydrosilylene complex was isolated as a single product by irradiation with periodic removal of CO. Crystal structure analyses and NMR spectroscopy of the η^5C_5Me_4Et derivative of the hydrosilylene complex revealed the existence of strong hydrido-silylene interligand interaction, which was also supported by DFT calculation. The hydrido(hydrosilylene) complex reacted smoothly with various polar molecules such as ketones, enones, nitriles, oxiranes, etc. to give new types of addition products.3. Reactions of Phosphasilaferracyclopropane with Various Polar Molecules : Photoreaction of carbonyl(phosphinosilyl)iron complex at low temperature afforded phosphasilaferracyclopropane via CO dissociation. Phosphasilaferracyclopropane reacted with several organic molecules having polarized unsaturated bonds such as 4-(dimethylamino)pyridine, benzaldehyde, ketones, and enones to give insertion products with a five-membered chelate ring. It also reacted with various molecules having a polarized single bond E-H (E = O, S, N, and P) instantaneously at room temperature to afford silyl(hydrophosphine)iron complexes. Less