【作者】 苗慧；

【导师】 王绍武；

【作者基本信息】 安徽师范大学 ， 有机化学， 2015， 博士

【摘要】 本论文合成得到了一系列环己二胺桥联β-二亚胺类有机化合物Cy[NHC（Me）CHC（Me）NAr]₂(Cy=（1R,2R）-（-）-1,2-cyclohexyl,Ar=2,6-/Pr-₂C₆H₃（1）,Ar=2,6-Me-2C_-6H-₃（2）;Cy=（1S,2S）-（+）-1,2-cyclohexyl,Ar=2,6-Et₂C₆H₃（3）;Cy = Trans-1,2-cyclohexyl,Ar = 2,6-iPr₂C₆H₃(（4）和手性环环己胺桥联β-酮亚胺有机化合物Cy[NC（Me）CHC（OH）（Me）]₂（Cy=（1R,2R）-（-）-1,2-cyclohexyl）（5）,并以此类化合物为配体,研究了其与三烷基稀土配合物RE[CH₂SiMe₃]₃（THF）₂或四配位三价稀土胺化物[（Me₃Si）₂N]₃REⅢ（μ-Cl）Li（THF）₃的反应性能,通过烷基或硅胺基消除反应,合成了系列新型稀土配合物,进一步研究了此类配合物在有机合成中的应用或磁性质。主要结果如下:1.手性环己二胺桥联二亚胺化合物H₂L（1）与1当量的三烷基稀土配合物RE[CH₂SiMe₃]₃（THF）₂,在己烷中,通过烷基消除反应,合成了单烷基手性稀土配合物{Cy[NC（Me）CHC（Me）NAr]₂}RECH₂SiMe₃[RE = Dy（6）,Er（7）,Yb（8）,Y（9）]。这些配合物都经红外光谱、元素分析进行了表征,配合物9还进行了¹HNMR、¹³CNMR的表征,所有配合物经X-ray单晶衍射确定了结构。进一步研究了这类单烷基手性稀土配合物对烯胺分子内氢胺化/环化反应的催化活性。结果表明,该类配合物作为催化剂都能催化烯胺底物转化发生氢胺化/环化反应生成相应的环状胺化物,不同中心金属催化剂对底物的转化率影响不大,当催化剂用量达到3%时,就能得到90%以上的转化率,但催化底物转化为六元环明显比转化为五元环困难。2.手性环己二胺桥联二胺化合物H₂L（3）与1当量的四配位三胺基稀土配合物[（Me₃Si）₂N]₃RE^Ⅲ（μ-Cl）Li（THF）₃在甲苯中,通过硅胺基消除反应,合成了系列手性稀土胺化物{Cy[NC（Me）CHC（Me）NAr]₂}REN（SiMe₃）₂[RE = Nd（10）,Dy（11）,Yb（12）,Y（13）];手性环己二胺桥联二胺化合物H₂L（1）与1当量的四配位三胺基稀土配合物[（Me₃Si）₂N]₃RE^Ⅲ（μ-Cl）Li（THF）₃反应,合成了系列手性稀土胺化物{Cy[NC（Me）CHC（Me）NAr]₂}REN（SiMe₃）₂[RE = Nd（14）,Gd（15）,Dy（16）,Er（17）,Y（18）]。胺化物都经红外光谱、元素分析进行了表征,配合物13、18还进行了¹HNMR、¹³CNMR的表征,胺化物10-13经X-ray单晶衍射确定了结构。进一步研究了这类稀土胺化物对β-硝基烯或α,β-不饱和羰基化合物与二苯基氧膦的氢膦化反应活性。结果表明,该类配合物作为催化剂都能催化β-硝基烯和α,β-不饱和羰基化合物与二苯基氧膦顺利的发生氢膦化反应。连在苯环上的不同电性的取代基,会给取代β-硝基烯或α,β-不饱和羰基化合物与二苯基氧膦的氢膦化反应带来一定影响,但对产率的影响不大。取代β-硝基烯和α,β-不饱和羰基化合物与二苯基氧膦的氢膦化反应活性不同,与取代β-硝基烯相比,α,β-不饱和羰基化合物与二苯基氧膦的氢膦化反应活性高,反应快。3.环己二胺桥联二亚胺化合物H₂L（4）与1当量的四配位三胺基稀土配合物[（M₃Si）₂N]₃RE^Ⅲ（μ-Cl）Li（THF）₃在甲苯中通过硅胺基消除反应,合成得到系列稀土胺化物{Cy[NC（Me）CHC（Me）NAr]₂}REN（SiMe₃）₂[RE = Nd（19）,Sm（20）,Dy（21）,Er（22）,Y（23）]。这些配合物都经红外光谱、元素分析进行了表征,配合物23还进行了¹HNMR、¹³CNMR的表征,所有配合物经X-ray单晶衍射确定了结构。系统研究了这类稀土胺化物催化醛或酮与亚磷酸二乙酯发生氢膦酸酯化反应的活性。结果表明,该类配合物作为催化剂都能顺利的催化醛和酮与亚磷酸二乙酯发生氢膦酸酯化反应得到α-羟基磷酸酯化物,而且反应条件温和,催化剂用量少,产率高。4.手性环己二胺桥联酮亚胺有机化合物H₂L（5）与四配位三胺基稀土配合物[（Me₃Si）₂N]₃RE^Ⅲ（μ-Cl）Li（THF）₃按3:2当量比,在甲苯中反应,合成得到双核手性稀土配合物{Cy[NC（Me）CHCO（Me）]₂}₃RE₂[RE = Dy（24）,Eu（25）];同样条件下,手性环己二胺桥联酮亚胺有机化合物（5）与四配位三胺基稀土配合物[（Me₃Si）₂N]₃RE^Ⅲμ（-Cl）Li（THF）₃按4:3当量反应,得到三核手性稀土配合物{Cy[NC（Me）CHCO（Me）]₂}₃RE₃ {Cy[NC（Me）CHCO（Me）][NC（CH₂）CHCO（Me）]}[RE=Y（26）,Gd（27）];手性环己二胺桥联的酮二亚胺有机化合物H₂L（5）与四配位三胺基稀土配合物[（Me₃Si）₂N]₃YbⅢ（μ-Cl）Li（THF）₃按1:1当量反应,得到了四核手性稀土 配合物{Cy[NC（Me）CHCO（Me）]₂}₄（μ₂-Cl）₂（μ₃-Cl）₂Yb₄（28）;手性环己二胺桥联的酮二亚胺有机化合物H₂L（5）与四配位三胺基稀土配合物[（Me₃Si）₂N]₃Nd^Ⅲ（μ-Cl）Li（THF）₃按2:1当量反应,则合成了十核手性稀土配合物{Li（Cy[NC（Me）CHCO（Me）]₂）₂Nd}₁₀（29）。实验结果表明,配体与稀土金属的投料比例显著影响着产物的结构。这些配合物都经红外光谱、元素分析进行了表征,配合物26还进行了¹HNMR的表征,所有配合物经X-ray单晶衍射确定了结构。进一步研究了双核手性稀土配合物24和环状十核手性稀土配合物29进行了磁性质,结果表明配合物24的实部磁化率（χ’）和虚部磁化率（χ"）对频率都表现出了一定的依赖性,具有单分子磁体的特点。更多还原

【Abstract】 A series of cyclohexyl bridged bis（β-diketiminato）compounds Cy[NHC（Me）CHC（Me）NAr]₂（Cy =（1R,2R）-（-）-1,2-cyclohexyl,Ar = 2,6-iPr₂C₆H₃（1）,Ar = 2,6-Me₂C₆H₃（2）;Cy =（1S,2S）-（+）-1,2-cyclohexyl,Ar = 2,6-Et₂C₆H₃（3）;Cy = Trans-1,2-cyclohexyl,Ar = 2,6-iPr₂C₆H₃（4））and Cy[NC（Me）CHC（OH）（Me）]₂（Cy =（1R,2R）-（-）-1,2-cyclohexyl）（5）were synthesized in good yields.Treatment of cyclohexyl bridged bis（β-diketiminato）or β-ketoiminate ligands with[（Me₃Si）₂N]₃RE^Ⅲ（μ-Cl）Li（THF）₃ afforded series of novel rare earth metal complexes bearing cyclohexyl bridged bis（β-diketiminato）or P-ketoiminate ligands in good yields.Application in organic synthesis or magnetic properties of the above rare earth metal complexes has also been further examined.The thesis consists of the following sections:1.A series of novel five coordinate rare earth metal alkylides with general formula{Cy[NC（Me）CHC（Me）NAr]₂}RECH₂SiMe₃[RE = Dy（6）,Er（7）,Yb（8）,Y（9）]were synthesized in good yields via reaction of RE[CH₂SiMe₃]₃（THF）₂ with the corresponding chiral diamine Cy[NHC（Me）CHC（Me）NAr]₂（Cy =（1R,2R）-（-）-1,2-cyclohexyl,Ar = 2,6-iPr₂C₆H₃（1））.The structures of all complexes were determined by single-crystal X-ray analyses.The catalytic activity of complexes 6-9 for the hydroamination/cyclization of aminoalkenes were evaluated,and results indicated that the complexes exhibited high catalytic activity and good enantioselectivity,afforded Markovnikov products.Under the same amount of catalyst and reaction temperature,the construction of a nitrogen-containing six-membered heterocyclic ring required a longer reaction time.2.A series of five coordinate rare earth metal amides with general formula{Cy[NC（Me）CHC（Me）NAr]₂}REN（SiMe₃）₂[RE = Nd（10）,Dy（11）,Yb（12）,Y（13）]were synthesized in good yields via reaction of[（Me₃Si）₂N]₃REm（μ-Cl）Li（THF）₃ with the corresponding chiral diamine Cy[NHC（Me）CHC（Me）NAr]₂（Cy =（1S,2S）-（+）-1,2-cyclohexyl,Ar = 2,6-Et₂C₆H₃（3））.Reaction of[（Me₃Si）₂N]₃RE^Ⅲ（μ-Cl）Li（THF）₃ with the chiral cyclohexyl bridged bis（β-diketiminato）compound 1 also afforded the corresponding rare earth metal amides with general formula {Cy[NC（Me）CHC（Me）NAr]₂}REN（SiMe₃）₂[RE=Nd（14）,Gd（15）,Dy（16）,Er（17）,Y（18）]in good yields.All compounds were fully characterized by spectroscopic methods and elemental analyses.The structures of complexes 10-13 were determined by single-crystal X-ray analyses.The catalytic activities of rare-earth complexes for diphenyphosphine oxide to β-nitroalkene or a,p-unsaturated carbonyl derivatives were investigated.The results indicated that all complexes exhibited a high catalytic activity towards the addition of diphenyphosphine oxide to β-nitroalkene and a,P-unsaturated carbonyl derivatives.3.Reaction of[（Me₃Si）₂N]₃RE^Ⅲ（μ-Cl）Li（THF）₃ with the trans-cyclohexyl bridged bis（β-diketiminato）compound 4 gave a series of rare earth metal amides with general formula {Cy[NC（Me）CHC（Me）NAr]₂}REN（SiMe₃）₂[RE = Nd（19）,Sm（20）,Dy（21）,Er（22）,Y（23）]in good yields.All compounds were fully characterized by spectroscopic methods and elemental analyses.The structures of all complexes were determined by single-crystal X-ray analyses.Catalytic activities of complexes 19-23 for hydrophosphonylation of aldehydes and ketones were developed,and results showed that these complexes exhibited a high catalytic activity towards the hydrophosphonylation of aldehydes and ketones in the presence of a very low loading of rare-earth metal amides at room temperature in a short time.4.Reaction of rare-earth metal[（Me₃Si）₂N]₃RE（μ-Cl）Li（THF）3 with 3/2 equiv of chiral ligand Cy[NC（Me）CHC（OH）（Me）]₂（Cy =（1R,2R）-（-）-1,2-cyclohexyl）（5）produced two oxygen-bridged dinuclear rare-earth metal complexes{Cy[NC（Me）CHCO（Me）]₂}₃RE₂[RE = Dy（24）,Eu（25）].Reaction of rare-earth metal[（Me₃Si）₂N]₃RE（μ-Cl）Li（THF）₃ with 4/3 equiv of chiral ligand 5 produced two oxygen and nitrogen-bridged trinuclear rare-earth metal complexes{Cy[NC（Me）CHCO（Me）]₂}₃RE₃ {Cy[NC（Me）CHCO（Me）][NC（CH₂）CHCO（Me）]}[RE = Y（26）,Gd（27）].Reaction of rare-earth metal[（Me₃Si）₂N]₃Yb（μ-Cl）Li（THF）₃ with 1 equiv of chiral ligand 5 produced chlorine and oxygen-bridged tetranuclear ytterbium complexe {Cy[NC（Me）CHCO（Me）]₂}₄（μ₂-Cl）₂（μ₃-Cl）₂Yb₄（28）.Reaction of rare-earth metal[（Me₃Si）₂N]₃RE（μ-Cl）Li（THF）3 with 2 equiv of chiral ligand 5 produced mixed polynuclear neodymium complex{Li（Cy[NC（Me）CHCO（Me）]₂）₂Nd}₁₀（29）.All compounds were fully characterized by spectroscopic methods and elemental analyses.The structures of all complexes were determined by single-crystal X-ray analyses.Preliminary studies revealed that complex 24 have the behavor of Single-Molecular Magnets.更多还原