膦硫及羧酸配体稳定下钌化合物的配位反应与结构表征

发布时间：2018-12-20 22:05

【摘要】：有机钌化合物因为其在催化加氢、脱硫等方面有广泛的应用价值而引起广泛的研究兴趣,所以本文设计与合成了一系列膦硫和羧酸配体稳定下的钌化合物,对结构新颖的钌化合物进行了核磁、红外和单晶衍射表征。2-氨基吡啶经过与二苯基氯化磷的反应得到有机膦化合物(Ph_2PNHpy),再进一步与硫族元素单质反应,得到相应的配体[Ph_2P(Q)NHpy](Q=O,S,Se),这些配体分别与[Ru(DMSO)4Cl_2]或[RuCl_2(η~6-p-cymene)]2等钌原料在四氢呋喃或者甲苯中加热回流得到系列钌化合物[Ru(PPh_3)_2Cl_2(κ~1-N-Ph_2P(S)NHpy)](1)、[Ru(DMSO)_2Cl_2(κ~1-N-Ph_2P(S)NHpy)](2)、[Ru(η~6-p-cymene)Cl(κ~2-N,N-Ph_2P(S)Npy)](3)、[Ru(THT)_2Cl_2(κ~1-N-Ph_2P(S)NHpy)](4)、[Ru(η~6-benzene)Cl_2(κ~1-N-Ph_2P(S)NHpy)](5)、[Ru(η~6-p-cymene)Cl(κ~2-N,N-Ph_2P(O)Npy)](6)、[Ru(η~6-benzene)Cl_2(κ~1-N-Ph_2P(O)NHpy)](7)、[Ru(η~6-p-cymene)Cl(κ~2-N,N-Ph_2P(Se)Npy)](8)和[Ru(η~6-benzene)Cl_2(κ~1-N-Ph_2P(Se)NHpy)](9)。其中对钌化合物3和5分别利用X-射线衍射测定了其晶体结构,核磁共振谱和红外光谱进行了谱学表征,探索了配合物3和5在常压下催化苯乙酮的加氢反应。2-甲基丙烯酸-3-三甲氧基硅烷丙基酯在Et_3N存在的条件下与[RuCl_2(PPh_3)_3]反应,由于酯基官能团的断裂,得到含有17e的中性的环状的钌化合物[RuCl_2{κ2-O,O-O_2CC=CH_2(CH3)}(PPh_3)_2](10),2-氯苯甲酸与[RuCl_2(PPh_3)_3]在同样类似的反应条件下作用得到也是17e的羧酸钌化合物[RuCl_2(κ2-O,O-O_2CC_6H_4-2-Cl)(PPh_3)_2](11),配合物2中先加入两个当量的正丁基锂,在Et_3N的条件下在加入SO_2,得到18e的钌化合物[Et_3NH][RuCl(SO_2)(κ2-C,O-C_6H_4-2-CO_2)(PPh_3)_2](12),同样地,加入[Et_4N]Cl则可以得到配合物[Et_4N]2[RuCl_2(κ2-C,O-C_6H_4-2-CO_2)(PPh_3)_2](13),对这四种配合物分别进行了核磁共振谱、红外光谱、质谱和元素分析等谱学表征,利用X-射线衍射测定了其晶体结构。用B3LYP方法分别对配合物10-13进行了分子轨道的计算。
[Abstract]:Organic ruthenium compounds have been widely used in catalytic hydrogenation and desulfurization. Therefore, a series of phosphine sulfur and carboxylic ligand stabilized ruthenium compounds have been designed and synthesized in this paper. The novel ruthenium compounds were characterized by NMR, IR and single crystal diffraction. 2-aminopyridine reacts with diphenyl phosphorus chloride to produce organic phosphine compounds (Ph_2PNHpy), and further reacts with sulfur elements. The corresponding ligands [Ph_2P (Q) NHpy] (QUOOONSSES) have been obtained, and the corresponding ligands [Ph_2P (Q) NHpy] have been obtained. A series of ruthenium compounds [Ru (PPh_3) _ 2Cl_2 (魏 ~ 1-)] were prepared by heating and refluxing with [Ru (DMSO) 4Cl_2] or [RuCl_2 (畏 ~ 6-p-cymene)] 2 in tetrahydrofuran or toluene, respectively. N-Ph_2P (S) NHpy)] (1), [Ru (DMSO) _ 2Cl_2 (魏 ~ 1-N-Ph_2P (S) NHpy)] (2), [Ru (畏 ~ 6-p-cymene) Cl (魏 ~ 2-NPh _ 2P (S) Npy)] (3), [Ru (THT) _ 2Cl_2 (魏 ~ 1-N-Ph_2P (S) NHpy)] (4), [Ru (畏 ~ 6-benzene) Cl_2 (魏 ~ 1-N-Ph_2P (S) NHpy)] (5), Ru (畏 ~ 6-p-cymene) Cl (魏 ~ 2-N), [Ru (畏 ~ 6-benzene) Cl_2] (5), [Ru _ 2Cl_2 (魏 ~ 1-N-Ph_2P (S) NHpy)] (4), [Ru (畏 ~ 6-benzene) Cl_2 (魏 ~ 1-N-Ph_2P (S) NHpy)] (5)] N-Ph_2P (O) Npy)] (6), [Ru (畏 ~ 6-benzene) Cl_2 (魏 ~ 1-N-Ph_2P (O) NHpy)] (7), Ru (畏 ~ 6-p-cymene) Cl (魏 ~ 2-N), N-Ph_2P (Se) Npy)] (8) and [Ru (畏 ~ 6-benzene) Cl_2 (魏 ~ 1-N-Ph_2P (Se) NHpy)] (9). The crystal structure, NMR and IR spectra of ruthenium compounds 3 and 5 were characterized by X-ray diffraction. The hydrogenation of acetophenone catalyzed by complexes 3 and 5 at atmospheric pressure was investigated. The reaction of 2-methacrylate with [RuCl_2 (PPh_3) _ 3] in the presence of Et_3N was studied. Due to the cleavage of the ester functional groups, a neutral cyclic ruthenium compound containing 17e was obtained [RuCl_2 {魏 2-O- O-O _ 2CCX CH2 (CH3)} (PPh_3) _ 2] (10). Under the same reaction conditions, 2-chlorobenzoic acid reacted with [RuCl_2 (PPh_3) _ 3] under the same reaction conditions to obtain a 17e ruthenium carboxylate compound [RuCl_2 (魏 2-O), O-O_2CC_6H_4-2-Cl) (PPh_3) _ 2] (11), the complex 2 was first added with two equivalent lithium Ding Ji, and SO_2, was added under the condition of Et_3N. A ruthenium compound of 18 e [Et_3NH] [RuCl (SO_2) (魏 2-CnO-Ctip _ 6H _ T _ 4-2-COS _ 2) (PPh_3) _ 2] (12) was obtained, similarly, By adding [Et_4N] Cl, the complex [Et_4N] 2 [RuCl_2 (魏 2-CUO-Ctip _ 6H4-2-COSP _ 2) (PPh_3) _ 2] (13) was obtained. The four complexes were characterized by nuclear magnetic resonance spectroscopy (NMR). The crystal structure was characterized by IR, MS and elemental analysis. The molecular orbitals of complex 10-13 were calculated by B3LYP method.
【学位授予单位】：安徽工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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