广西师范大学硕士学位论文含NH官能团Ni(Ⅱ)配合物的合成及其不对称催化氢化性能研究姓名：张玉贞申请学位级别：硕士专业：无机化学指导教师：陈自卢;梁福沛20070501含NH官能团Ni(Ⅱ)配合物的合成及其不对称催化氢化性能研究中文摘要2004级无机化学研究生：张玉贞指导教师：陈自卢博士梁福沛教授以过渡金属配合物为催化剂催化氢化羰基化合物是近几十年来比较活跃的一个课题。

特别是从上世纪90年代以来，对于后过渡金属（如Rh、Ru、Ir）含NH官能团配合物的催化研究更是取得了突破性进步。

日本Noyori因在此方面的卓越成就而荣获2001年诺贝尔化学奖。

含NH官能团配合物的催化研究目前主要集中在贵金属（如Rh、Ru、Ir）。

而对于3d 金属NH官能团配合物的催化性能研究还非常罕见。

本论文合成了一系列Ni(Ⅱ)的NH官能团配合物，对其结构进行了表征，并且选取其中6种配合物检测其催化性能。

1．NiCl2与配体乙二胺（en）、邻苯二胺（opda）和N, N, N’, N’-四甲基乙二胺（tmen）反应得到了三种新配合物：[Ni(en)(2,2′-bipy)(H2O)2]Cl2（1）, [Ni(en)(H2O)2(tmen)]Cl2·2H2O （2）, [Ni(opda)(Phen)Cl2]· CH3OH（3）。

配合物（1）属单斜晶系，P21/c空间群，晶胞参数为：a = 14.132(5) Å, b = 8.371(3) Å, c = 15.454(6) Å, β = 115.734(5)°；配合物（2）属正交晶系，P bcn空间群，晶胞参数为：a = 15.005(4) Å, b = 9.591(3) Å, c = 12.505(3) Å；配合物（3）属单斜晶系，C2/c空间群，晶胞参数分别为：a = 13.898(4) Å, b = 18.246(5) Å, c = 10.015(3) Å, β = 126.313(3) °。

2．NiCl2与环己烷乙二胺（dach）和（R, R）-1、2-二苯基乙二胺[(R, R)-dpen] 反应得到了六个新配合物：[Ni(dach)(tmen)(H2O)2]Cl2·2H2O（5），[Ni(dach)(2,2′-bipy)2(Cl)2]·2H2O （6），[Ni2((R, R)-dpen)4(H2O)2Cl2]Cl2·CH3CH2OCH3（8），[Ni((R, R)-dpen)(phen)(CH3OH)2]Cl2（9），[Ni2(dach)2(phen)2 (Cl)2(H2O)2]Cl2（10）, [Ni((R,R)-dpen)(tmen)(H2O)2]Cl2（11）。

配合物（5）属正交晶系，I ba2空间群，晶胞参数为：a = 14.160(2) Å, b = 9.8435(14) Å, c = 15.221(2) Å；配合物（6）属单斜晶系，C2/c空间群，晶胞参数为：a = 15.270(15) Å, b =17.732(17) Å, c = 10.244(10) Å, β = 127.535(10)°。

配合物（8）属三斜晶系，P1空间群，晶胞参数为：a = 19.738(7) Å, b =10.439(8) Å, c = 16.418(12) Å, α =105.044(11)°，β = 98.591(10)°，γ =90.003(11) °。

配合物（9）属单斜晶系，C2/c空间群，晶胞参数为：a = 15.270(15) Å, b = 17.732(17) Å, c = 10.244(10) Å, β = 127.535(10)°，配合物（10）属单斜晶系，P21/n空间群，晶胞参数为：a =12.378(3) Å, b = 13.836(3) Å, c = 21.279(5) Å, β = 101.273(3)°。

配合物（11）属三斜晶系，P1空间群，晶胞参数为：a = 9.017(3) Å, b =11.690(4) Å, c = 13.095(5) Å, α = 77.431(4)°，β = 89.984(4) °，γ =69.298(5)°。

3． NiCl2与配体1，8-萘二胺(dant)反应得到配合物 [Ni2(dant)4(DMF)2Cl2]Cl2·3H2O （12），同N, N, N’, N’-四乙基乙二胺反应得到二乙酰基亚胺(datm)的配合物 [Ni(datm)2]（14）。

另外MnCl2同邻啡罗啉和乙二胺反应，得到一个有机超分子（13）[phen2(en)]n。

其中配合物（12）和（14）同属单斜晶系，P21/c空间群，晶胞参数分别为（12）：a = 15.0758(10) Å, b = 22.7726(15) Å, c = 16.3817(11)Å, β = 113.3880(10)°；（14）：a = 8.822(2) Å, b = 11.832(3) Å, c = 15.635(3) Å, β= 119.190(3)°。

有机超分子（13）属三方晶系，P1空间群，晶胞参数为：a = 7.6518(8) Å, b = 9.8985(10) Å, c = 10.6525(11) Å,α = 69.492(2)°, β = 70.416(2)°, γ= 80.602(2)°。

4．选取配合物（3）、（4）、（8）、（9）、（12）与（15）（其中配合物15为已报道配合物）为催化剂检验其不对称催化氢化效果。

本论文利用这些配合物做催化剂，分别以三种不同的氢源进行催化氢化测试：一、以氢气为氢源的催化离子氢化；二、以异丙醇为氢源的氢转移氢化；三、以甲酸-三乙胺为氢源的氢转移氢化。

反应产物通过气相色谱检验。

结果表明：这几种配合物对苯乙酮的催化离子氢化效果比较明显，其中配合物（12）在KOH 条件下催化底物苯乙酮的转化率达到72.1%。

而对于以异丙醇和甲酸-三乙胺为氢源的氢转移氢化催化效果较差，转化率几乎为零。

关键词：不对称催化、Ni（Ⅱ）配合物、晶体结构、NH官能团、二胺配体Synthesis of Nickel Complexes Containing NH Functionality and their Appication in Asymmetric CatalysisAbstractPostgraduate: Yu-Zhen Zhang Supervisors: Dr. Zi-Lu ChenProf.Fu-Pei LiangIn recent decades, asymmetric catalysis of unsaturated compounds containing carbonyl group has attracted much attention. Especially since 1990s, the study on asymmetric catalysis using late transition metal (Rh, Ru, Ir) complexes containing NH functionality has made a rapid progress. Noyori won the Nobel Prize in 2001 for his excellent study on asymmetric catalysis.In the reported studies about asymmetric catalysis using transition metal complexes containing NH functionality as catalysts are mainly concentrated on expensive metals, such as Rh、Ru、Ir. Much less studies were made on 3d transition metals. Our aim in this work is to use the much cheaper metal Ni as the metal center to synthesize the similar catalysts contaning NH functionalities and to investigate their catalytic hydrogenation of ketones. In this thesis, we have managed to synthesize a series of nickel complexes, and six among of them were selected to study the catalysis of hydrogenation of ketones.1. The reactions of NiCl2 with ethylenediamine (en), o-phenylene diamine (opda), or N,N,N’,N’-tetramethylethylenediamine (tmen) gave [Ni(en)(2,2′-bipy)(H2O)2]Cl2(1), [Ni(en)(H2O)2(tmen)]Cl2·2H2O (2) and[Ni(opda)(Phen)Cl2]CH3OH (3), respectively. Complex 1 crystallizes in the monoclinic space group P21/c with a = 14.132(5) Å, b = 8.371(3) Å, c = 15.454(6) Å, β = 115.734(5)°. Complex 2 crystallizes in the Orthorhombic space group P bcn with a = 15.005(4) Å, b = 9.591(3) Å, c = 12.505(3) Å. Complex 3 crystallizes in the monoclinic space group C2/c with a = 13.898(4) Å, b = 18.246(5) Å, c = 10.015(3) Å, β = 126.313(3) °.2. The reactions using NiCl2 and diaminocyclohexane (dach) or (R, R)-(+)-1,2- diphenylenediamine ((R, R)-dpen) as the main starting materials provided [Ni(dach)(tmen)(H2O)2]Cl2·2H2O (5), [Ni(dach)(2,2′-bipy)2(Cl)2]·2H2O (6), [Ni2((R, R)-dpen)4(H2O)2Cl2]Cl2·CH3CH2OCH3(8), [Ni((R,R)-dpen)(phen)(CH3OH)2]Cl2 (9), [Ni2((R, R)-dpen)2(phen)2(Cl)2(H2O)2]Cl2(10) and[Ni((R,R)-dpen)(tmen)(H2O)2]Cl2(11). Complex 5 crystallizes in the Orthorhombic space group I bam with a = 14.160(2) Å, b = 9.8435(14) Å, c =15.221(2) Å. Complex 6 crystallizes in the monoclinic space group C2/c with a = 15.270(15) Å,b = 17.732(17) Å,c = 10.244(10) Å, β = 127.535(10)°. Complex 8 crystallizes in the Triclinic space group P1with a = 9.738(7) Å, b = 10.439(8) Å, c = 16.418(12) Å, α = 105.044(11)°，β = 98.591(10)°, γ = 90.003(11)°. Complex 9 crystallizes in the monoclinic space group C2/c with a= 15.270(15) Å, b = 17.732(17) Å, c = 10.244(10) Å, β = 127.535(10)°. Complex 10 crystallizes in the monoclinic space group P21/n with a = 12.378(3) Å, b = 13.836(3) Å, c = 21.279(5) Å, β = 1101.273(3)°. Complex 11 crystallizes in the Triclinic space group Pīwith a = 9.017(3) Å, b = 11.690(4) Å, c = 13.095(5) Å, α = 77.431(4)°, β = 89.984(4)°, γ = 69.298(5)°.3. Another three compounds [Ni2(dant)4(DMF)2Cl2]Cl2·3H2O (12), [en(phen)24H2O]Cl2 (14) and [Ni(datm)2] (13) were isolated from the reactions of NiCl2 with 1,8-diaminonaphthalene (dant) or diacetamide (datm): 12 and 14 crystallize in the monoclinic space group P21/c with a = 15.0758(10) Å, b = 22.7726(15) Å, c = 16.3817(11) Å, β = 113.3880(10)° for 12 and a = 8.822(2) Å, b = 11.832(3) Å, c = 15.635(3) Å, β= 119.190(3)° for 14. 13 crystallizes in the triclinic space group P1 with a = 7.6518(8) Å, b = 9.8985(10) Å, c = 10.6525(11) Å,α = 69.492(2)°, β = 70.416(2)°, γ= 80.602(2)°.4. Complexes 3, 4, 8, 9, 12 and 15 were selected to perform the asymmetric catalytic hydrogenation of ketones. Three kinds of asymmetric catalytic hydrogenation were carried out: (a) catalytic ionic hydrogenations using H2 as hydrogen source, (b) transfer hydrogenation using isopropanol as hydrogen source, (c) transfer hydrogenation using formic acid-triethylamine as hydrogen source. The products are checked by GC. The results revealed that these complexes show nice catalytic effects in catalytic ionic hydrogenations. Among of them a 72.1% conversion of acetophenone into the corresponding alcohol was found in the catalytic hydrogenation of ketone using complex 12 as catalyst. However they present nearly no catalytic effects in transfer hydrogenation using both isopropanol and formic acid-triethylamine as hydrogen source.Keywords: Asymmetric catalysis, Nickel(II)Complex, Crystallography, NH Functionality, Diamine ligand张玉贞广西师范大学硕士学位论文 2007论文独创性声明本人郑重声明：所提交的学位论文是本人在导师的指导下进行的研究工作及取得的成果。