【摘要】：過渡金屬氫化物是一類重要的金屬有機化合物,在催化化學、合成化學和化學工業(yè)等各個領(lǐng)域有廣泛的應(yīng)用。人們已經(jīng)合成出了一系列的過渡金屬氫配合物,并且發(fā)現(xiàn)很多的金屬氫化物在烯烴、炔烴、CO2、羰基化合物的活化還原以及醇的脫氫反應(yīng)中有很好的催化效果。其中又以含有釕、銠、銥等貴金屬的氫化物居多,相對比而言廉價金屬來源更加廣泛,對環(huán)境也更加友好;因此探索可以替代的廉價金屬的氫化物成為新的研究熱點。到目前為止,已有很多關(guān)于廉價金屬氫化物的制備以及催化應(yīng)用的報道,尤其是鐵氫配合物;已有文獻報道部分鐵氫配合物在催化應(yīng)用中具有與貴金屬氫化物相似的催化活性;關(guān)于鈷氫配合物直接參與催化反應(yīng)的報道雖少,但根據(jù)已報道的文獻可知,鈷氫配合物是多種催化反應(yīng)的活性中間體,具有極大的發(fā)展?jié)摿�。本論文主要從以下兩部分展開,第一部分我們研究了 Co(PMe3)4與苯硒酚、鄰甲基苯硒酚、對甲氧基苯硒酚的反應(yīng),成功得到了四種新型的含硒配位的有機鈷配合物1-4。對Co(PMe3)4與苯硒酚系列配體反應(yīng)的機理進行了探究,同時新型的鈷氫配合物7通過PhSeLi,CoCl(PMe3)3以及PhSH三組分反應(yīng)得到。通過對新合成的含硒配位的有機鈷配合物的性質(zhì)進行探索,發(fā)現(xiàn)鈷氫配合物2對醛酮的硅氫化反應(yīng)有一定的催化效果,配合物3、4可以與CO進一步反應(yīng)得到雙羰基鈷配合物5和6。第二部分在實驗室已有的實驗成果基礎(chǔ)上對(o-PPh2)PhSeH與Fe(PMe3)4反應(yīng)得到的鐵氫配合物進行系統(tǒng)的性質(zhì)探索,從鐵氫配合物與CO的反應(yīng)中,我們分離出了含有兩種異構(gòu)體的羰基鐵氫配合物8;鐵氫配合物與乙酰丙酮的反應(yīng),經(jīng)過單晶衍射驗證生成了雙螯合鐵配合物11。此外,我們研究了(o-PPh2)PhSeH 與 Co(PMe3)4、CoCl(PMe3)3、CoMe(PMe3)4 的反應(yīng),均得到雙螯合鈷配合物14。
[Abstract]:Transition metal hydride is an important class of organometallic compounds, which has been widely used in catalytic chemistry, synthetic chemistry and chemical industry. A series of transition metal hydrogen complexes have been synthesized and many metal hydride have been found to have good catalytic effects in the activation and reduction of alkenes alkynes and CO2, carbonyl compounds as well as the dehydrogenation of alcohols. Among them, the hydride containing ruthenium, rhodium, iridium and other precious metals is more common, compared with cheap metal sources more extensive, more environmentally friendly; therefore, the exploration of cheap metals can be replaced by hydride has become a new research hotspot. Up to now, there have been a lot of reports on the preparation and catalytic application of cheap metal hydride, especially the iron hydrogen complexes, and some of the iron hydrogen complexes have similar catalytic activity to the noble metal hydride in the catalytic application. Although there are few reports on the direct participation of cobalt hydrogen complexes in catalytic reactions, according to the reported literature, the cobalt hydrogen complexes are active intermediates of various catalytic reactions and have great potential for development. In the first part, we studied the reaction of Co (PMe3) 4 with phenylselenol, o-methylphenylselenol and p-methoxyphenylselenol, and successfully obtained four new organic cobalt complexes 1-4 containing selenium. The mechanism of the reaction of Co (PMe3) 4 with phenylselenol ligands was investigated. A new cobalt hydrogen complex 7 was obtained by the reaction of PhSeLi,CoCl (PMe3) 3 and PhSH. By exploring the properties of the newly synthesized organic cobalt complexes containing selenium, it is found that cobalt hydrogen complex 2 has a certain catalytic effect on the hydrosilylation of aldehydes and ketones. Complex 3H4 can be further reacted with CO to obtain cobalt bicarbonyl complexes 5 and 6. In the second part, based on the experimental results in the laboratory, the properties of the ferric hydrogen complexes obtained by the reaction of (o-PPh2) PhSeH with Fe (PMe3) 4 were investigated systematically, and the reaction of the ferric hydrogen complexes with CO was carried out. The carbonyl iron hydrogen complex 8 containing two isomers was isolated. The reaction of ferric hydrogen complex with acetylacetone was studied and the double chelate iron complex 11 was obtained by single crystal diffraction. In addition, the reaction of (o-PPh2) PhSeH with Co (PMe3) _ 4 Cocl (PMe3) _ 3 (PMe3) _ 4 has been studied.
【學位授予單位】：山東大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4

【參考文獻】

相關(guān)博士學位論文 前1條

1 周紅衛(wèi);三甲基膦支持的新型鐵、鈷、鎳氫化合物的合成及性質(zhì)研究[D];山東大學;2015年

，

本文編號：2369634