CN108579816B - 轴向配体修饰的同核双金属化合物催化剂及其制法和应用 - Google Patents
轴向配体修饰的同核双金属化合物催化剂及其制法和应用 Download PDFInfo
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Abstract
本发明公开了一种轴向配体修饰的同核双金属化合物催化剂及其制法和应用。所述轴向配体修饰的同核双金属化合物催化剂的制备方法包括:将包含Rh2(esp)2、轴向配体和有机溶剂的混合体系于室温下反应,获得轴向配体修饰的同核双金属化合物催化剂,其中,所述轴向配体包括含不饱和氮元素的有机配体。本发明提供的轴向配体修饰的同核双金属化合物催化剂在通过轴向配位调节双核铑金属化合物的反应活性和选择性,相比于改变桥联配体,操作方法更加简便,合成步骤更加简捷,配位后不但不影响Rh2(esp)2的反应活性,反而提高了催化合成N‑H杂环丙烷化合物的反应选择性,而且也有普适性。
Description
技术领域
本发明特别涉及一种轴向配体修饰的同核双金属化合物催化剂及其制法和应用,属于催化剂制备技术领域。
背景技术
Rh2(esp)2作为一种独特的同核双金属化合物,在金属核之间存在着铑-铑键,在催化有机反应时,往往呈现出与单核金属化合物不同的反应方式,Rh2(esp)2对催化合成碳烯和氮宾物种具有较高的催化活性,然而Rh2(esp)2的价格非常昂贵,对催化合成某些N-H杂环丙烷化合物的反应中选择性低。
发明内容
本发明的主要目的在于提供一种轴向配体修饰的同核双金属化合物催化剂及其制法和应用,以克服现有技术的不足。
为实现前述发明目的,本发明采用的技术方案包括:
本发明实施例提供了一种轴向配体修饰的同核双金属化合物催化剂的制备方法,其包括:将包含Rh2(esp)2、轴向配体和有机溶剂的混合体系于室温下反应,获得轴向配体修饰的同核双金属化合物催化剂,其中,所述轴向配体包括含不饱和氮元素的有机配体。
本发明实施例还提供了由所述的制备方法制备形成的轴向配体修饰的同核双金属化合物催化剂。
本发明实施例还提供了由所述的制备方法制备形成的轴向配体修饰的同核双金属化合物催化剂或所述的轴向配体修饰的同核双金属化合物催化剂于N-H丙环类化合物合成反应中的应用。
与现有技术相比,本发明的优点包括:
(1)本发明实施例提供的轴向配体修饰的同核双金属化合物催化剂,首次通过轴向配体修饰后的Rh2(esp)2催化剂应用于催化合成N-H杂环丙烷的反应中;
(2)本发明实施例提供的轴向配体修饰的同核双金属化合物催化剂,Rh2(esp)2-L在催化合成N-H杂环丙烷的反应中的催化活性和选择性均高于单纯的Rh2(esp)2,而且具有普适性;
(3)本发明实施例提供的轴向配体修饰的同核双金属化合物催化剂,合成条件温和,原料廉价易得,且反应速度快,相比于通过桥联配体改变双核铑金属化合物的特性避免了繁琐的合成步骤。
附图说明
图1是本发明实施例1中咪唑、2-甲基咪唑和2,4-二甲基咪唑修饰的Rh2(esp)2的X光电子能谱图;
图2是本发明实施例1中咪唑、2-甲基咪唑和2,4-二甲基咪唑修饰的Rh2(esp)2的傅里叶变换红外光谱图;
图3a和图3b是咪唑与Rh2(esp)2配位之后的化学结构示意图;
图4a和图4b是2-甲基咪唑与Rh2(esp)2配位之后的化学结构示意图;
图5a和图5b是2,4-二甲基咪唑与Rh2(esp)2配位之后的化学结构示意图;
图6是本发明一典型实施例中一种轴向配体修饰的同核双金属化合物催化剂的化学结构示意图。
具体实施方式
鉴于现有技术中的不足,本案发明人经长期研究和大量实践,得以提出本发明的技术方案。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。
本发明实施例提供了一种轴向配体修饰的同核双金属化合物催化剂的制备方法,其包括:将包含Rh2(esp)2、轴向配体和有机溶剂的混合体系于室温下反应,获得轴向配体修饰的同核双金属化合物催化剂,其中,所述轴向配体包括含不饱和氮元素的有机配体。
具体的,所述的制备方法包括:向Rh2(esp)2的有机溶剂溶液中加入轴向配体,直至溶液的颜色由绿色变为浅红色,获得所述轴向配体修饰的同核双金属化合物催化剂。
进一步的,所述轴向配体的用量远大于Rh2(esp)2的用量。
进一步的,所述轴向配体与Rh2(esp)2的摩尔比不小于2∶1。
进一步的,所述含不饱和氮元素的有机配体包括咪唑类配体、吡啶类配体以及恶唑啉中的任意一种或两种以上的组合,但不限于此。
进一步的,所述咪唑类配体包括咪唑、2-甲基咪唑或者2,4-二甲基咪唑;所述吡啶类配体包括吡啶、3-甲基吡啶或者2,6-二甲基吡啶,但不限于此。
进一步的,所述的制备方法包括:向Rh2(esp)2的有机溶剂溶液中加入轴向配体,并在转速为400~500rpm的条件下持续搅拌0.1h以上,获得所述轴向配体修饰的同核双金属化合物催化剂。
进一步的,所述的制备方法还包括:对反应后的混合体系于25℃-50℃的真空干燥烘箱中进行干燥处理以获得轴向配体修饰的同核双金属化合物催化剂。
进一步的,所述有机溶剂包括二氯甲烷、甲醇中的任意一种,但不限于此。
本发明实施例还提供了由所述的制备方法制备形成的轴向配体修饰的同核双金属化合物催化剂。
进一步的,所述轴向配体与Rh2(esp)2的配位关系的摩尔比2∶1。
进一步的,所述轴向配体修饰的同核双金属化合物催化剂为均相催化剂。
更进一步的,所述轴向配体修饰的同核双金属化合物催化剂是通过轴向配体与Rh2(esp)2轴向配位影响铑周围的电子排布进而影响双核铑金属配合物的催化特性。
本发明实施例还提供了由所述的制备方法制备形成的轴向配体修饰的同核双金属化合物催化剂或所述的轴向配体修饰的同核双金属化合物催化剂于N-H丙环类化合物合成反应中的应用。
一直以来,对双核铑金属化合物的研究主要都是通过改变桥连配体来影响金属化合物的特性和反应活性,桥连配体种类很多并且对双核铑金属核上的电荷密度影响显著。但是,通过改变轴向配体也可以对双核铑金属化合物进行细微的调节,这种调节作用可在一些反应中提高金属化合物的反应活性,尤其是可以实现不同的反应选择性。这种通过轴向配体的调节与通过改变桥连配体来调节双核铑金属化合物的活性相比,操作更加简便,基本上不需要合成步骤。
具体的,在一些较为具体的实施方案中,所述的制备方法包括:
在室温下配置3.8mg/mL的Rh2(esp)2的二氯甲烷溶液,呈现出澄清的绿色溶液,取10mL上述溶液并向其中逐渐加入轴向配体,在室温下使用磁力搅拌器充分搅拌,直至溶液的颜色会由绿色逐渐变为红色,待溶液颜色不再变化即可判定为配位完全,萃取出过量的轴向配体;将配位后的Rh2(esp)2的二氯甲烷溶液悬蒸干燥即得到轴向配体配位后的Rh2(esp)2催化剂,标记为Rh2(esp)2-L。本发明实施例提供的制备方法,不仅操作简单快捷,而且制备的轴向配体修饰后的Rh2(esp)2催化剂对催化N-H杂环丙烷化合物具有较高的选择性和普适性。
本发明是基于配位化学策略,选用Rh2(esp)2为中心活性分子,以咪唑、2-甲基咪唑、2,4-二甲基咪唑、吡啶、恶唑啉等为原料,通过含不饱和氮元素的有机配体与Rh2(esp)2发生轴向配位,影响了金属的分子轨道排布,可以使得铑-铑金属键变得更长,进而调节某些反应的选择性成为可能;具体的,含不饱和氮元素的咪唑类有机配体与铑元素发生轴向配位,配体与Rh2(esp)2轴向配位后影响了铑周围的电荷排布,从而可以影响在某些反应中的催化选择性通过调节不同的轴向配体,轴向配体修饰后的Rh2(esp)2催化剂的化学结构示意图如图6所示,以及试验工艺条件,实现对Rh2(esp)2进行微调作用,获得轴向配体修饰的Rh2(esp)2催化剂,即Rh2(esp)2-L催化剂(即轴向配体修饰的Rh2(esp)2催化剂),其有望在有机催化方面得到广泛的应用。
如下将结合附图以及具体实施例对该技术方案、其实施过程及原理等作进一步的解释说明。
实施例1:轴向配体修饰的Rh2(esp)2催化剂的制备:
步骤1:在室温下配置3.8mg/mL的Rh2(esp)2的二氯甲烷溶液;
步骤2:取10mL上述溶液并向其中逐渐加入不同轴向配体(参阅表1),在室温下使用磁力搅拌器充分搅拌,溶液的颜色会由绿色逐渐变为红色,待溶液颜色不再变化即可判定为配位完全,萃取出过量的轴向配体,将配位后的Rh2(esp)2的二氯甲烷溶液悬蒸干燥即得轴向配体修饰(配位)后的Rh2(esp)2催化剂,标记为Rh2(esp)2-L。其中轴向配体咪唑、2-甲基咪唑和2,4-二甲基咪唑修饰的Rh2(esp)2的X光电子能谱图如图1所示;轴向配体咪唑、2-甲基咪唑和2,4-二甲基咪唑修饰的Rh2(esp)2的傅里叶变换红外光谱图如图2所示;配位后的结构式图请分别参阅图3a-图5b。
其中,所述轴向配体的摩尔用量应大于Rh2(esp)2的2倍。
实施例2:将所述Rh2(esp)2-L应用于催化合成N-H杂环丙烷化合物的过程如下:
该反应在10mL的反应瓶中进行,称取0.55mmol的2,4-二硝基苯基羟胺,0.005mmolRh2(esp)2-L化剂加入到反应瓶中,用油泵抽真空后再充入氮气,如此抽换三次,再用注射器加入5.0mL的2,2,2-三氟乙醇溶剂,以及0.50mmol的2-甲基-1-苯基丙烯,室温条件下反应2h。反应产物取清液0.60μL,用气相色谱仪对反应产物进行定量分析,结果如表1:
表1为不同的轴向配体与Rh2(esp)2轴向配位对催化性能的影响
注:L为轴向配体
试验结果显示,对于催化合成N-H杂环丙烷化合物,Rh2(esp)2-L催化剂的选择性高于Rh2(esp)2催化剂。
本发明实施例通过轴向配位的方法构建高选择性的轴向配体修饰的Rh2(esp)2催化剂,即Rh2(esp)2-L,可有效解决Rh2(esp)2催化剂催化合成N-H杂环丙烷化合物选择性低的问题,同时也可以更好地利用双核铑贵金属催化剂。
以上实施例制备工艺中所涉及的各类中间产物和最终产物(以下统称为“样品”)可通过以下手段进行结构表征:
采用Perkin Elmer PHI 5000ESCT System X-射线光电子能谱仪,以PdKa(1486.6eV)为发射源,测量时分析室压力为10-9torr,通能为46.95eV,结合能采用污染C的标准结合能(CIS=284.6eV)进行校正;
采用Bruker SMART APEX II型X-射线单晶衍射仪上进行样品化合物结构式的分析。
实施例3:轴向配体修饰的Rh2(esp)2催化剂的制备
本实施例中轴向配体修饰的Rh2(esp)2催化剂的制备过程与实施例1基本一致,不同之处在于本实施例中采用Rh2(esp)2的甲醇溶液。
将获得的Rh2(esp)2-L应用于催化合成N-H杂环丙烷化合物的过程和结果可参照实施例2。
应当理解,上述实施例仅为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (1)
1.一种N-H丙环类化合物的合成方法,其特征在于包括:以轴向配体修饰的同核双金属化合物催化剂作为合成N-H丙环类化合物的催化剂,
所述轴向配体修饰的同核双金属化合物催化剂的制备方法包括:于室温下,向Rh2(esp)2的有机溶剂溶液中加入轴向配体,并在转速为400~500rpm的条件下持续搅拌0.1h以上,直至溶液的颜色由绿色变为浅红色,对反应后的混合体系于25℃-50℃的真空干燥烘箱中进行干燥处理以获得轴向配体修饰的同核双金属化合物催化剂,
其中,所述轴向配体与Rh2(esp)2的摩尔比不小于2:1,所述轴向配体包括含不饱和氮元素的有机配体,所述含不饱和氮元素的有机配体包括咪唑类配体、吡啶类配体以及恶唑啉中的任意一种或两种以上的组合,所述有机溶剂包括二氯甲烷、甲醇中的任意一种,所述咪唑类配体包括咪唑、2-甲基咪唑或者2,4-二甲基咪唑;所述吡啶类配体包括吡啶、3-甲基吡啶或者2,6-二甲基吡啶。
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