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

1.我们发展了一种无给体的硅（亚硅基）铁配合物Cp^*Fe（CO）（=SiMes_2）SiMe_3（1）的热合成和光化学合成方法，并测定了它的X射线晶体结构。在CO存在下，1在80℃热反应，得到二硅烷基配合物Cp^*Fe（CO）_2SiMeMesSiMe_2Mes（2a）及其异构体2b。2a或2b的光解定量地再现了1。这些结果为硅（亚硅基）配合物中极其容易的1，2-和1，3-基团迁移反应提供了最直接的证据。类似地，我们发现在（芳基硅基）钨配合物上，在碱存在下，硅基配体上的芳基发生1，2-迁移到配位不饱和的金属中心，得到碱稳定的亚硅基配合物.氢化硅基钨配合物的合成、结构和反应性：Cp^*（CO）_3WMe与空间位阻三氢钨的光反应 关于我们 在密封管中用硅烷H_3SiC（SiMe_3）_3反应，得到了含硅化合物和含硅化合物的混合物。通过对硅氢化物的η^5C_5Me_4Et衍生物的晶体结构和核磁共振谱的分析，发现硅氢化物中存在较强的配体间相互作用，这一结果也得到了DFT计算的支持。该配合物能与酮、烯酮、腈、环氧乙烷等极性分子顺利反应，生成新型加成产物.磷硅铁环丙烷与不同极性分子的反应：羰基（膦基硅基）铁配合物在低温下的光反应通过CO解离得到磷硅铁环丙烷。磷硅铁环丙烷与4-（二甲氨基）吡啶、苯甲醛、酮、烯酮等具有极性不饱和键的有机分子反应，得到了具有五元螯合环的插入产物。在室温下，它还能与具有极性单键E-H（E = O，S，N，P）的各种分子瞬间反应，得到硅基（氢膦）铁配合物。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