二茂铁亚胺环钯化合物有序自组装纳米薄膜催化碳碳偶联反应机理
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摘要
绿色、经济、可持续的化学过程是当今化学领域的主要挑战之一。非均相催化剂具有易于分离、高效回收等特点，俨然已经成为绿色化学研究的重要手段。但是，在非均相催化领域仍存在许多急需解决的问题，尤其是在非均相催化剂的作用机理研究方面一直都存有争议。目前，高速发展的合成技术和新颖的分析手段为科学家对机理的研究提供更为有利的条件，使得非均相催化机理的研究得以进一步发展。
纳米薄膜材料由于具有易于分离、回收，便于重复使用，分析方法简单等特点，使其在非均相催化应用中极具吸引力。与此同时，把催化剂分子均匀地负载在重现性好、易于表征的界面上能够更深入的对非均相催化行为进行研究。因此，制备并利用合适的纳米催化薄膜材料，借助有效的表征和分析手段对界面催化过程进行系统的研究具有重要的理论意义和应用价值。
本论文利用Langmuir-Blodgett膜、自组装膜和聚合物刷的方法制备了环钯化合物纳米薄膜，并以Suzuki-Miyaura反应为模板，借助有效的科研手段，对基于分子层面的非均相催化过程中的界面催化行为进行了系统的研究。具体研究内容及成果如下：
1.制备了不同的表面压下的二茂铁亚胺环钯化合物1（图1）的单层膜和LB膜，并应用到非均相催化Suzuki-Miyaura反应体系。通过紫外可见光谱（UV）和原子力显微镜（AFM）分析表明不同表面压下所制备的LB膜呈现出不同的表面形貌。与在表面压为14,18,26,30mN/m制备的催化剂LB膜相比，在表面压为22mN/m时制备的LB膜表现出更高的催化效率。实验结果表明LB膜催化效率与催化剂分子排列取向有关，即LB膜内分子排列有序和取向规整更有利于催化反应的进行。Figure1The structure of cyclopalladated ferrocenylimine1.
探讨了二茂铁亚胺环钯化合物1的LB膜在催化过程中的结构和化学变化。通过小角X射线衍射光谱（LXRD）和AFM图像变化分析推测催化过程。结果证明，催化开始阶段底物和碱与催化剂表面接触生成氧化加成中间产物是整个催化过程的主要步骤。结合X光电子能谱(XPS)对LB膜催化反应机理分析可知，反应物与LB膜内的Pd活性中心相结合并产生中间体。中间体随着反应的进行转化为产物从LB膜的表面逐渐释放以生成产物。（图2）Figure2Illustration of the catalytic reaction mechanism of the cross-coupling reaction of4-iodobenzoic acid with arylboronic acid catalyzed by catalyst1LB films.
2.通过共价接枝的方法分别在硅片、玻璃和石英表面成功制备了高效、重复性好、稳定性高的二茂铁亚胺环钯化合物自组装膜(Si-CDI-Pd)（图3）。以Suzuki-Miyaura反应为模板，在一定温度的条件下，Si-CDI-Pd在水相中无需其他配体即可表现出较高催化活性、选择性和宽的底物适用性。此自组装催化薄膜在痕量钯浸出的情况下，至少可以循环8次，展现出良好的可重复性和稳定性。Figure3Preparation of cyclopalladated ferrocenylimine catalystic films (Si-CDI-Pd).
利用循环伏安法（CV）、水接触角（WCA）、AFM和XPS对不同反应时间的催化过程进行分析，阐明了在Si-CDI-Pd表面发生的PdII到Pd0和Pd0到PdII的循环过程(图4)，并提出Si-CDI-Pd催化Suzuki-Miyaura反应是一个表面Pd0起作用的非均相表面催化过程。整个反应是催化剂和底物协同生成目标产物的过程，且分子之间有序密集排列引起催化剂间的协同效应增强了整体催化效率。Figure4High-resolution XPS spectra of Pd3d, B1s and Br3d from the silicon wafer surfaces ofSi-CDI-Pd with different reaction time.
3.通过原子转移自由基聚合的方法制备了N-羟甲基丙烯酰胺聚合物刷，并将芳香亚胺环钯化合物成功地接枝到聚合物刷表面制备出聚合物刷催化薄膜（Si-PHAM-Pd[I]）（图5）。并通过表面形貌和结构的表征证明芳香亚胺环钯化合物是以共价键形式接枝到聚合物刷表面。Figure5Synthesis of the cyclopalldated arylimine PHAM-brushes (Si-PHAM-Pd[I]).
Si-PHAM-Pd[I]能够有效催化Suzuki-Miyaura反应，表现出增强的催化活性、高的底物适用性、选择性和良好的稳定性。能够在基本没有催化剂浸出的情况下，经过5次循环仍能得到90%的偶联产物。随着循环实验的进行催化活性有所降低，可能是因为芳香亚胺环钯化合物中的十八烷基链在反应过程中缠绕在聚合物刷表面或和聚合物刷柔性链相互缠绕，降低了催化活性中心和底物的接触几率。（图6）Figure6Yields and TOF obtained with recycled catalyst of Si-PHAM-Pd[I].
4.为了通过改变聚合物刷表面和界面的催化微环境，提高它的催化性能，作者通过在聚合物刷表面接枝不同结构的环钯催化剂，制备了二茂铁亚胺环钯化合物功能化的聚合物刷催化薄膜（Si-PHAM-Pd[II]）（图7）。催化结果表明：与Si-PHAM-Pd[I]相比，Si-PHAM-Pd[II]能够更有效地催化Suzuki-Miyaura反应，且表现出良好的循环使用性和稳定性，几乎没有Pd的浸出的情况下至少可以循环催化8次。Figure7Preparation of cyclopalladated ferrocenylimines functionalized PHAM-brushes catalyticfilm (Si-PHAM-Pd[II]).
通过WCA、CV、AFM和XPS对催化Suzuki-Miyaura反应过程的表面形貌和化学变化的分析得出其反应机理：整个催化循环为PdII到Pd0和Pd0的PdII的过程（图8），催化过程中零价钯和溴苯氧化加成反应生成中间产物，整个反应是催化剂和反应物协同在功能化的聚合物刷表面完成的。Figure8High-resolution XPS spectra of Pd3d, B1s and Br3d from the silicon wafer surfacesgrafted Si-PHAM-Pd[II].
5.首次用原子转移自由基聚合的方法制备了丙烯酰基二茂铁环钯单体聚合物刷（Pd/PBs）（图9）。通过和上述催化体系比较，对催化剂微环境的变化对催化活性的影响进行初步探讨。实验结果表明：Pd/PBs的催化活性表现为高于均相，低于Si-CDI-Pd和Si-PHAM-Pd[II]的情况。推测可能是由于丙烯酰基二茂铁环钯单体（3a）的大位阻结构，使聚合物刷表面有序排列降低；3a树枝状的刚性结构使聚合物刷的伸展性降低，两点原因共同造成其较弱的催化活性。Figure9Preparation of the poly (Acroloyl cyclopalladated ferrocenylimines) brushes (Pd/PBs).
紫外光谱和循环伏安法表明Pd/PBs的稳定性较差。这可能是由于3a内酯基在碱性条件催化的Suzuki-Miyaura反应中发生水解，从而使催化剂脱落。因此，作者拟通过使用柔性链或稳定的醚键取代酯基的催化剂作为聚合单体，从而达到提高聚合物刷的稳定性和催化活性的目的。
Green, economical, sustainable chemical process is one of the main challengesin today's chemistry. Heterogeneous catalyst is consistent with the requirements ofgreen chemistry because of waste reduction, atom economy and efficient recycling.However, there are still many challengs to be solved in the field of heterogeneouscatalysis. Especially for the mechanism of the catalyst system has been disputed.Rapid development of synthetic technology and novel analysis methods provide amore favorable condition for scientists, which makes the investigation of catalyticmechanism be in the ascendant.
Nano-catalysis film, as a kind of heterogeneous catalyst, is considered to be oneof the most fascinating topics in green chemistry due to its easy separation, reuse andsimple characterization. Heterogeneous catalytic behavior can be strengthenedthrough immobilized catalyst molecules onto solid surfaces which were easy tocharacterize. Therefore, design and preparations of nano-catalysis film, along with thesystematic studies of interface catalytic behaviors with the help of effective, scientificmeans become a very important research topic.
In this paper, nano-films of cyclopalladated complexes were prepared by usingLangmuir-Blodgett technology, self-assembled monolayers and polymer brushes.Taken Suzuki-Miyaura reaction as a template, systematic study of the interfacecatalytic behavior were carried in heterogeneous catalytic processes by effectiveresearch tools, which enable us to understand the mechanism of heterogeneouscatalysis based on the molecular level. The main contents are listed:
1. The monolayer and LB films of cyclopalladated ferrocenylimine1(Figure1)were prepared at different surface pressure and applied for Suzuki–Miyaura reactionsin heterogeneous catalytic system. Morphology studies of monolayer prepared atdifferent surface pressure were investigated by atomic force microscope (AFM),which showed that the surface morphologies of the LB films at different surfacepressure were significantly different. LB films of cyclopalladated ferrocenylimine1prepared at surface pressure of22mN/m showed the highest catalytic efficiencies compared with that at14,18,26,30mN/m. These results demonstrated that thecatalytic efficiency was related to the molecular arrangement of the catalysts.Figure1The structure of cyclopalladated ferrocenylimine1.
The structure changes of cyclopalladated ferrocenylimine1LB films bylow-angle X-ray diffraction (LAXD) as well as the film surface morphologicalchanges by AFM in catalytic process were also investigated. The results indicatedthat the substrate and base were contacting with the catalyst to cover the catalyst filmsurface at the beginning of catalytic process, which is the key step in whole process.The whole catalytic process included constantly contacting and covering the surfaceof the catalyst to generate Pd intermediates that could be transferred into the product,which were further identified by the X-ray photoelectron emission microscopy (XPS)analysis.Figure2Illustration of the catalytic reaction mechanism of the cross-coupling reaction of4-iodobenzoic acid with arylboronic acid catalyzed by catalyst1LB films.
2. In order to investigate the heterogeneous catalysis mechanism, an efficient,reusable and stable catalyst nano-sheet film (Si-CDI-Pd) was developed, in whichcyclopalladated ferrocenylimines were grafted onto silicon, glass or quartz surfacesby covalent.(Figure3) The catalysts films were tested in Suzuki-Miyaura reactionand displayed high activity for the preparation of various biaryls at elevatedtemperatures in neat water without ligands. Good reusability and stability were presented as reused at least8times with little Pd leaching into the crude product.Figure3Preparation of cyclopalladated ferrocenylimine catalystic films (Si-CDI-Pd).
The reasonable and feasible reaction mechanism based on the results of AFM,XPS characterizations and CV tests of different reaction time were deeply explored,in which a cycle of PdIIto Pd0and Pd0to PdIIon the surface was clearly detected andillustrated. Pd0on the surface of nano-sheet film as an active surface acted asheterogeneous catalyst to catalyze the coupling reaction.(Figure4) The wholereaction was cooperative process of the catalyst and substrate. The synergistic effectof catalysts enhanced the catalysts catalytic efficiency due to the order arrangementmolecules.Figure4High-resolution XPS spectra of Pd3d, B1s and Br3d from the silicon wafer surfaces ofSi-CDI-Pd with different reaction time.
3. Cyclopalladated arylimine functionalized polymer brushes (Si-PHAM-Pd[I])were also obtained by reacting PHAM-brushes with N, N-Carbonyldiimidazole (CDI)and cyclopalladated arylimine.(Figure5) The surface morphology and chemistrystructure which were characterized by contact angle method, AFM and XPS showedthat cyclopalladated arylimines were modified onto solid surfaces by covalent bond. Figure5Synthesis of the cyclopalldated arylimine PHAM-brushes (Si-PHAM-Pd[I]).
Si-PHAM-Pd[I] had good catalytic activity in heterogeneous compared tohomogeneous catalyst and exhibited much improved stability and recyclability overtimes in Suzuki-Miyaura reaction. In recycle experiments, high yield (~90%) of theproducts was retained after five runs. However, catalystic activities ofSi-PHAM-Pd[I] gradully decreased in six run. It was proposed that the accessibilityof substrates to the catalytic active center became weaker due to the winding andaggregation of octadecyl chain.(Figure6)Figure6Yields and TOF obtained with recycled catalyst of Si-PHAM-Pd[I].
4. The microenvironment of the polymer brush surface and interface had beenchanged by graftting of the different structure of catalyst on the surface of polymerbrush film in order to improve the catalytic performation. Cyclopalladatedferrocenylimine functionalized polymer brushes film (Si-PHAM-Pd [II]) wasdeveloped onto silicon, glass and quartz surfaces by covalent bond. Si-PHAM-Pd [II]was tested in Suzuki-Miyaura reaction and displayed high activity for the preparationof various biaryls at elevated temperatures in neat water without ligands. Improvedreusability and stability are presented as that catalytic film can be reused at least8 times with little Pd leaching into the crude product.Figure7Preparation of cyclopalladated ferrocenylimines functionalized PHAM-brushes catalyticfilm (Si-PHAM-Pd[II]).
The reasonable and feasible reaction mechanism of the heterogeneousSuzuki-Miyaura reaction was deeply explored by CV, AFM and XPS, in which thewhole reaction occurred on the surface of the functionalized polymer brush by thecoordination of catalyst and reactant. The bromobenzene oxidative addition withpalladium (0) had been proven in the catalytic process, and the catalytic cycle of PdIIto Pd0and Pd0to PdIIon the surface was clearly detected and illustrated. In thisapproach, Pd (0) on the surface of nano-films as an active species acted asheterogeneous catalyst to catalyze coupling reaction proceeds via a mechanism thatwas proposed for the surface-catalyzed process.Figure8High-resolution XPS spectra of Pd3d, B1s and Br3d from the silicon wafer surfacesgrafted Si-PHAM-Pd[II].
5. Poly (Acroloyl cyclopalladated ferrocenylimines) brushes (Pd/PBs) wasprepared by atom transfer radical polymerization successfully, which was the firsttime of the synthesis of organometallic polymer brushes. By comparing with theprevious catalytic system, the changes of the catalytic microenvironment influence oncatalytic activity were discussed. Pd/PBs exhibits improved catalytic activity than the homogeneous catalyst in Suzuki-Miyaura reaction, but lower than that of Si-CDI-Pdand Si-PHAM-[II]. That might be due to the large steric hindrance of acroloylcyclopalladated ferrocenylimines in the polymer brushes, which exhibited lower orderarrangement of surface and reduced the flexibility of polymer brushes.Figure9Synthesis of the poly (Acroloyl cyclopalladated ferrocenylimines) brushes (Pd/PBs).
Pd/PBs exhibited poor stability which was proved by ultraviolet spectroscopyand cyclic voltammetry. It was because of the existence of ester group in3a, whichhydrolyzed under the base solution in Suzuki-Miyaura reaction. Other catalystmonomer with flexible chain, stable ester group will be replaced for polymer, whichmay be improved for the stability and catalytic activity of the polymer brushes infuture.
纳米薄膜材料由于具有易于分离、回收，便于重复使用，分析方法简单等特点，使其在非均相催化应用中极具吸引力。与此同时，把催化剂分子均匀地负载在重现性好、易于表征的界面上能够更深入的对非均相催化行为进行研究。因此，制备并利用合适的纳米催化薄膜材料，借助有效的表征和分析手段对界面催化过程进行系统的研究具有重要的理论意义和应用价值。
本论文利用Langmuir-Blodgett膜、自组装膜和聚合物刷的方法制备了环钯化合物纳米薄膜，并以Suzuki-Miyaura反应为模板，借助有效的科研手段，对基于分子层面的非均相催化过程中的界面催化行为进行了系统的研究。具体研究内容及成果如下：
1.制备了不同的表面压下的二茂铁亚胺环钯化合物1（图1）的单层膜和LB膜，并应用到非均相催化Suzuki-Miyaura反应体系。通过紫外可见光谱（UV）和原子力显微镜（AFM）分析表明不同表面压下所制备的LB膜呈现出不同的表面形貌。与在表面压为14,18,26,30mN/m制备的催化剂LB膜相比，在表面压为22mN/m时制备的LB膜表现出更高的催化效率。实验结果表明LB膜催化效率与催化剂分子排列取向有关，即LB膜内分子排列有序和取向规整更有利于催化反应的进行。Figure1The structure of cyclopalladated ferrocenylimine1.
探讨了二茂铁亚胺环钯化合物1的LB膜在催化过程中的结构和化学变化。通过小角X射线衍射光谱（LXRD）和AFM图像变化分析推测催化过程。结果证明，催化开始阶段底物和碱与催化剂表面接触生成氧化加成中间产物是整个催化过程的主要步骤。结合X光电子能谱(XPS)对LB膜催化反应机理分析可知，反应物与LB膜内的Pd活性中心相结合并产生中间体。中间体随着反应的进行转化为产物从LB膜的表面逐渐释放以生成产物。（图2）Figure2Illustration of the catalytic reaction mechanism of the cross-coupling reaction of4-iodobenzoic acid with arylboronic acid catalyzed by catalyst1LB films.
2.通过共价接枝的方法分别在硅片、玻璃和石英表面成功制备了高效、重复性好、稳定性高的二茂铁亚胺环钯化合物自组装膜(Si-CDI-Pd)（图3）。以Suzuki-Miyaura反应为模板，在一定温度的条件下，Si-CDI-Pd在水相中无需其他配体即可表现出较高催化活性、选择性和宽的底物适用性。此自组装催化薄膜在痕量钯浸出的情况下，至少可以循环8次，展现出良好的可重复性和稳定性。Figure3Preparation of cyclopalladated ferrocenylimine catalystic films (Si-CDI-Pd).
利用循环伏安法（CV）、水接触角（WCA）、AFM和XPS对不同反应时间的催化过程进行分析，阐明了在Si-CDI-Pd表面发生的PdII到Pd0和Pd0到PdII的循环过程(图4)，并提出Si-CDI-Pd催化Suzuki-Miyaura反应是一个表面Pd0起作用的非均相表面催化过程。整个反应是催化剂和底物协同生成目标产物的过程，且分子之间有序密集排列引起催化剂间的协同效应增强了整体催化效率。Figure4High-resolution XPS spectra of Pd3d, B1s and Br3d from the silicon wafer surfaces ofSi-CDI-Pd with different reaction time.
3.通过原子转移自由基聚合的方法制备了N-羟甲基丙烯酰胺聚合物刷，并将芳香亚胺环钯化合物成功地接枝到聚合物刷表面制备出聚合物刷催化薄膜（Si-PHAM-Pd[I]）（图5）。并通过表面形貌和结构的表征证明芳香亚胺环钯化合物是以共价键形式接枝到聚合物刷表面。Figure5Synthesis of the cyclopalldated arylimine PHAM-brushes (Si-PHAM-Pd[I]).
Si-PHAM-Pd[I]能够有效催化Suzuki-Miyaura反应，表现出增强的催化活性、高的底物适用性、选择性和良好的稳定性。能够在基本没有催化剂浸出的情况下，经过5次循环仍能得到90%的偶联产物。随着循环实验的进行催化活性有所降低，可能是因为芳香亚胺环钯化合物中的十八烷基链在反应过程中缠绕在聚合物刷表面或和聚合物刷柔性链相互缠绕，降低了催化活性中心和底物的接触几率。（图6）Figure6Yields and TOF obtained with recycled catalyst of Si-PHAM-Pd[I].
4.为了通过改变聚合物刷表面和界面的催化微环境，提高它的催化性能，作者通过在聚合物刷表面接枝不同结构的环钯催化剂，制备了二茂铁亚胺环钯化合物功能化的聚合物刷催化薄膜（Si-PHAM-Pd[II]）（图7）。催化结果表明：与Si-PHAM-Pd[I]相比，Si-PHAM-Pd[II]能够更有效地催化Suzuki-Miyaura反应，且表现出良好的循环使用性和稳定性，几乎没有Pd的浸出的情况下至少可以循环催化8次。Figure7Preparation of cyclopalladated ferrocenylimines functionalized PHAM-brushes catalyticfilm (Si-PHAM-Pd[II]).
通过WCA、CV、AFM和XPS对催化Suzuki-Miyaura反应过程的表面形貌和化学变化的分析得出其反应机理：整个催化循环为PdII到Pd0和Pd0的PdII的过程（图8），催化过程中零价钯和溴苯氧化加成反应生成中间产物，整个反应是催化剂和反应物协同在功能化的聚合物刷表面完成的。Figure8High-resolution XPS spectra of Pd3d, B1s and Br3d from the silicon wafer surfacesgrafted Si-PHAM-Pd[II].
5.首次用原子转移自由基聚合的方法制备了丙烯酰基二茂铁环钯单体聚合物刷（Pd/PBs）（图9）。通过和上述催化体系比较，对催化剂微环境的变化对催化活性的影响进行初步探讨。实验结果表明：Pd/PBs的催化活性表现为高于均相，低于Si-CDI-Pd和Si-PHAM-Pd[II]的情况。推测可能是由于丙烯酰基二茂铁环钯单体（3a）的大位阻结构，使聚合物刷表面有序排列降低；3a树枝状的刚性结构使聚合物刷的伸展性降低，两点原因共同造成其较弱的催化活性。Figure9Preparation of the poly (Acroloyl cyclopalladated ferrocenylimines) brushes (Pd/PBs).
紫外光谱和循环伏安法表明Pd/PBs的稳定性较差。这可能是由于3a内酯基在碱性条件催化的Suzuki-Miyaura反应中发生水解，从而使催化剂脱落。因此，作者拟通过使用柔性链或稳定的醚键取代酯基的催化剂作为聚合单体，从而达到提高聚合物刷的稳定性和催化活性的目的。
Green, economical, sustainable chemical process is one of the main challengesin today's chemistry. Heterogeneous catalyst is consistent with the requirements ofgreen chemistry because of waste reduction, atom economy and efficient recycling.However, there are still many challengs to be solved in the field of heterogeneouscatalysis. Especially for the mechanism of the catalyst system has been disputed.Rapid development of synthetic technology and novel analysis methods provide amore favorable condition for scientists, which makes the investigation of catalyticmechanism be in the ascendant.
Nano-catalysis film, as a kind of heterogeneous catalyst, is considered to be oneof the most fascinating topics in green chemistry due to its easy separation, reuse andsimple characterization. Heterogeneous catalytic behavior can be strengthenedthrough immobilized catalyst molecules onto solid surfaces which were easy tocharacterize. Therefore, design and preparations of nano-catalysis film, along with thesystematic studies of interface catalytic behaviors with the help of effective, scientificmeans become a very important research topic.
In this paper, nano-films of cyclopalladated complexes were prepared by usingLangmuir-Blodgett technology, self-assembled monolayers and polymer brushes.Taken Suzuki-Miyaura reaction as a template, systematic study of the interfacecatalytic behavior were carried in heterogeneous catalytic processes by effectiveresearch tools, which enable us to understand the mechanism of heterogeneouscatalysis based on the molecular level. The main contents are listed:
1. The monolayer and LB films of cyclopalladated ferrocenylimine1(Figure1)were prepared at different surface pressure and applied for Suzuki–Miyaura reactionsin heterogeneous catalytic system. Morphology studies of monolayer prepared atdifferent surface pressure were investigated by atomic force microscope (AFM),which showed that the surface morphologies of the LB films at different surfacepressure were significantly different. LB films of cyclopalladated ferrocenylimine1prepared at surface pressure of22mN/m showed the highest catalytic efficiencies compared with that at14,18,26,30mN/m. These results demonstrated that thecatalytic efficiency was related to the molecular arrangement of the catalysts.Figure1The structure of cyclopalladated ferrocenylimine1.
The structure changes of cyclopalladated ferrocenylimine1LB films bylow-angle X-ray diffraction (LAXD) as well as the film surface morphologicalchanges by AFM in catalytic process were also investigated. The results indicatedthat the substrate and base were contacting with the catalyst to cover the catalyst filmsurface at the beginning of catalytic process, which is the key step in whole process.The whole catalytic process included constantly contacting and covering the surfaceof the catalyst to generate Pd intermediates that could be transferred into the product,which were further identified by the X-ray photoelectron emission microscopy (XPS)analysis.Figure2Illustration of the catalytic reaction mechanism of the cross-coupling reaction of4-iodobenzoic acid with arylboronic acid catalyzed by catalyst1LB films.
2. In order to investigate the heterogeneous catalysis mechanism, an efficient,reusable and stable catalyst nano-sheet film (Si-CDI-Pd) was developed, in whichcyclopalladated ferrocenylimines were grafted onto silicon, glass or quartz surfacesby covalent.(Figure3) The catalysts films were tested in Suzuki-Miyaura reactionand displayed high activity for the preparation of various biaryls at elevatedtemperatures in neat water without ligands. Good reusability and stability were presented as reused at least8times with little Pd leaching into the crude product.Figure3Preparation of cyclopalladated ferrocenylimine catalystic films (Si-CDI-Pd).
The reasonable and feasible reaction mechanism based on the results of AFM,XPS characterizations and CV tests of different reaction time were deeply explored,in which a cycle of PdIIto Pd0and Pd0to PdIIon the surface was clearly detected andillustrated. Pd0on the surface of nano-sheet film as an active surface acted asheterogeneous catalyst to catalyze the coupling reaction.(Figure4) The wholereaction was cooperative process of the catalyst and substrate. The synergistic effectof catalysts enhanced the catalysts catalytic efficiency due to the order arrangementmolecules.Figure4High-resolution XPS spectra of Pd3d, B1s and Br3d from the silicon wafer surfaces ofSi-CDI-Pd with different reaction time.
3. Cyclopalladated arylimine functionalized polymer brushes (Si-PHAM-Pd[I])were also obtained by reacting PHAM-brushes with N, N-Carbonyldiimidazole (CDI)and cyclopalladated arylimine.(Figure5) The surface morphology and chemistrystructure which were characterized by contact angle method, AFM and XPS showedthat cyclopalladated arylimines were modified onto solid surfaces by covalent bond. Figure5Synthesis of the cyclopalldated arylimine PHAM-brushes (Si-PHAM-Pd[I]).
Si-PHAM-Pd[I] had good catalytic activity in heterogeneous compared tohomogeneous catalyst and exhibited much improved stability and recyclability overtimes in Suzuki-Miyaura reaction. In recycle experiments, high yield (~90%) of theproducts was retained after five runs. However, catalystic activities ofSi-PHAM-Pd[I] gradully decreased in six run. It was proposed that the accessibilityof substrates to the catalytic active center became weaker due to the winding andaggregation of octadecyl chain.(Figure6)Figure6Yields and TOF obtained with recycled catalyst of Si-PHAM-Pd[I].
4. The microenvironment of the polymer brush surface and interface had beenchanged by graftting of the different structure of catalyst on the surface of polymerbrush film in order to improve the catalytic performation. Cyclopalladatedferrocenylimine functionalized polymer brushes film (Si-PHAM-Pd [II]) wasdeveloped onto silicon, glass and quartz surfaces by covalent bond. Si-PHAM-Pd [II]was tested in Suzuki-Miyaura reaction and displayed high activity for the preparationof various biaryls at elevated temperatures in neat water without ligands. Improvedreusability and stability are presented as that catalytic film can be reused at least8 times with little Pd leaching into the crude product.Figure7Preparation of cyclopalladated ferrocenylimines functionalized PHAM-brushes catalyticfilm (Si-PHAM-Pd[II]).
The reasonable and feasible reaction mechanism of the heterogeneousSuzuki-Miyaura reaction was deeply explored by CV, AFM and XPS, in which thewhole reaction occurred on the surface of the functionalized polymer brush by thecoordination of catalyst and reactant. The bromobenzene oxidative addition withpalladium (0) had been proven in the catalytic process, and the catalytic cycle of PdIIto Pd0and Pd0to PdIIon the surface was clearly detected and illustrated. In thisapproach, Pd (0) on the surface of nano-films as an active species acted asheterogeneous catalyst to catalyze coupling reaction proceeds via a mechanism thatwas proposed for the surface-catalyzed process.Figure8High-resolution XPS spectra of Pd3d, B1s and Br3d from the silicon wafer surfacesgrafted Si-PHAM-Pd[II].
5. Poly (Acroloyl cyclopalladated ferrocenylimines) brushes (Pd/PBs) wasprepared by atom transfer radical polymerization successfully, which was the firsttime of the synthesis of organometallic polymer brushes. By comparing with theprevious catalytic system, the changes of the catalytic microenvironment influence oncatalytic activity were discussed. Pd/PBs exhibits improved catalytic activity than the homogeneous catalyst in Suzuki-Miyaura reaction, but lower than that of Si-CDI-Pdand Si-PHAM-[II]. That might be due to the large steric hindrance of acroloylcyclopalladated ferrocenylimines in the polymer brushes, which exhibited lower orderarrangement of surface and reduced the flexibility of polymer brushes.Figure9Synthesis of the poly (Acroloyl cyclopalladated ferrocenylimines) brushes (Pd/PBs).
Pd/PBs exhibited poor stability which was proved by ultraviolet spectroscopyand cyclic voltammetry. It was because of the existence of ester group in3a, whichhydrolyzed under the base solution in Suzuki-Miyaura reaction. Other catalystmonomer with flexible chain, stable ester group will be replaced for polymer, whichmay be improved for the stability and catalytic activity of the polymer brushes infuture.
引文
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