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

过渡金属/电子元素体系动态配合物的结构和功能

基本信息

批准号：
14078202
负责人：
TOBITA Hiromi
金额：
$ 15.36万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

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

1。对甲硅烷基和芳基（Silylene）复合物的1,2和1,3迁移反应的实验证据，我们开发了无供体的Silyl（Silylene）铁复合物CP^*Fe（CO）的热和光化学合成方法（= sime_2）Sime_3（= sime_2）Sime_3（1），并确定其X-ray Systal结构。在CO存在下，1在80℃的热反应给出了Diasilanyl复合物CP^*Fe（CO）_2Simemessime_2MES（2A）及其异构体2B。 2A或2B的光解会定量再现1。这些结果提供了最简单的证据，即在甲硅烷基（Sillylene）配合物中极为容易的1,2和1,3组迁移反应。同样，我们发现，在（芳基丁基史坦复合物上），在底莲配体上的芳基群进行了1,2个迁移到协调不饱和的金属中心的迁移，在碱有的存在的情况下，可以提供基础稳定的甲硅烷基络合物。在密封的管中，有更多的osilane h_3sic（sime_3）_3，在密封的管中获得了更多的osilane h_3sic（sime_3）_3，可提供氢化硅烷的混合物和甲硅烷基络合物。通过辐射，通过定期去除CO。晶体结构分析和NMR光谱法分离出Hydrosilylene络合物作为单个产物，对Hydrosilylene络合物的η^5C_5ME_4ET衍生物的NMR光谱法揭示了强氢甲基二甲苯互动的存在，这也通过DFT计算支持了。氢（Hydrosilylene）复合物与各种极性分子（例如酮，烯烃，硝酸盐，氧兰烷等）平稳反应，以提供新型的添加产品。3。磷酸氟丙烷与各种极性分子的反应：低温下羰基（磷酸硅烷基）铁复合物的光反应提供了通过CO解离提供的磷脂氟乙酰丙烷。磷酸二甲丙烷与几个具有极化不饱和键的有机分子反应，例如4-（二甲基氨基）吡啶，苯甲醛醛，酮和烯酮，并用五元成熟的樱桃环提供插入产物。它还与具有极化的单键E-H（E = O，S，N和P）的各种分子在室温下反应，以负担得起甲硅烷基（水膦）铁络合物。较少的