三甲基膦支持的新型铁、钴、镍氢化合物的合成及性质研究

发布时间：2018-08-27 14:50

【摘要】：过渡金属氢化物在金属有机化学领域中占有重要的地位,因为过渡金属氢化物是许多催化反应的重要中间体或者催化剂,例如,氢化反应、硅氢化反应、氢甲酰化反应以及氢转移反应。文献中有关铁氢、钴氢、镍氢化合物的合成和催化应用的报道很多,这些氢化物多数含有PCP、PNP型钳式配体。但是,文献中有关钴氢化合物催化醛酮硅氢化反应的例子极少。过渡金属氢化物另一个重要应用是过渡金属氢化物可以和碳碳三键发生插入反应,得到相应的烯基金属化合物,利用这一反应可以进行碳碳三键的功能化。文献中报道的有关过渡金属氢化物和碳碳三键的插入反应,主要是Ir、Os、Ru等贵金属。镍氢化合物和炔烃发生插入反应,生成烯基镍化合物的报道很少。我们利用CoMe(PMe3)4和N-亚苄基-1-萘胺反应,得到新型[CNC]型钴氢配合物1,配合物1与CH3I、EtBr反应,生成相应的卤化物2和3。然而,配合物1与Bronsted酸(HCl、TFA)反应生成新的钴氢配合物4和5。配合物1中的Co原子与萘环C原子之间的Co-C键被切断,用氘代实验验证了还原到萘环上的氢原子来源于HCl。配合物1与乙酰丙酮反应,得到一个意外的产物(配合物7)。我们对配合物7的生成,提出了可能的反应机理。配合物1可以催化醛酮的硅氢化反应,并具有较好的催化效果。我们设计合成了2-二苯基膦基苯硒酚,并用Ni(PMe3)4和此配体反应,得到镍氢配合物11,探索了配合物11与炔烃的反应。配合物11在室温下不稳定,采用原位生成配合物11的方法,然后与炔烃反应。配合物11与苯乙炔、1-苯基-1-丙炔反应,得到烯基镍配合物12、13。配合物11和二苯乙炔、三甲基硅乙炔、1-苯基-2-(三甲基硅基)乙炔反应,得到含有叶立德结构的镍杂环丙烷配合物14、15、16。2-二苯基膦基苯硒酚与Fe(PMe3)4反应,生成铁氢配合物17,配合物17在酸性介质中会生成双螯合配合物18。
[Abstract]:Transition metal hydrides play an important role in the field of organometallic chemistry because they are important intermediates or catalysts for many catalytic reactions, such as hydrogenation, hydrosilylation, hydroformylation and hydrogen transfer reactions. Most of these hydrides contain PCP, PNP-type clamp ligands. However, there are few examples of cobalt hydrides catalyzing the hydrosilylation of aldehydes and ketones in the literature. Another important application of transition metal hydrides is that transition metal hydrides can insert with carbon-carbon triple bonds to form corresponding olefin-based metal compounds. The first reaction can functionalize the C-C triple bond. The reported insertion reactions of transition metal hydrides and C-C triple bonds, mainly precious metals such as Ir, Os, Ru, etc., are rare. The insertion reactions of nickel hydrides with alkynes, resulting in the formation of alkenyl nickel compounds, are rare. We have obtained new products by the reaction of CoMe (PMe3) 4 with N-benzylidene-1-naphthylamine. Complex 1 reacts with C H3I and EtBr to form corresponding halides 2 and 3. However, complex 1 reacts with Bronsted acid (HCl, TFA) to form new cobalt-hydrogen complexes 4 and 5. The C o-C bonds between CO atoms in complex 1 and C atoms in naphthalene ring are cut off, and the hydrogen atoms reduced to naphthalene ring are confirmed to be derived from HCl by deuteration experiments. Complex 1 reacts with acetylacetone to produce an unexpected product (complex 7). We propose a possible reaction mechanism for the formation of complex 7. Complex 1 can catalyze the hydrosilylation of aldehydes and ketones with good catalytic effect. We designed and synthesized 2-diphenylphosphine phenylselenol and obtained it by the reaction of Ni (PMe3) 4 with this ligand. Nickel-hydrogen complex 11, which is unstable at room temperature, reacts with alkynes by in-situ formation of complex 11. Complex 11 reacts with phenylacetylene, 1-phenyl-1-propyne to obtain allyl nickel complexes 12,13. Complexes 11 and diphenylacetylene, trimethylsilylacetylene, 1-phenyl-2-(trimethylsilicon) Nickel heterocyclic propane complex 14,15,16.2-diphenylphosphine phenylselenophenol containing Yelide structure reacted with Fe(PMe3)4 to form iron-hydrogen complex 17. Complex 17 formed double chelate complex 18 in acidic medium.
【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：O641.4;O621.25

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