CN111362985B - 一种水溶性环状四核钯(ii)配合物及其制备方法和用途 - Google Patents
一种水溶性环状四核钯(ii)配合物及其制备方法和用途 Download PDFInfo
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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Abstract
本发明公开了一种水溶性的钯偶联催化剂—水溶性环状四核钯(Ⅱ)配合物及制备方法和用途，并初步评价催化偶联反应的活性。本发明的水溶性环状四核钯(II)配合物是以四个(R2CH2COO)Pd片段和R1NH‑配体桥联形成钯(Ⅱ)环状配合物，其制备方法包括在氮气气氛下，将PdCl2先后与胺、CO2的饱和溶液、Ba(OH)2、羧酸酐和乙酰胺反应得到羧酸·亚胺合钯(Ⅱ)四聚体白色粉末；采用溶剂扩散法得到目标化合物的单晶；目标化合物在水作溶剂中催化对2‑溴噻吩与对甲氧基苯硼酸之间的偶联反应为的转化率为87％，这对含水体系偶联反应催化剂的选择具有一定的指导意义。
Description
技术领域
本发明属于化学合成领域，具体涉及一种水溶性环状四核钯(II)配合物：羧酸·亚胺合钯(Ⅱ)四聚体水合物[Pd(NHR1)(R2CH2COO)]4·n(H2O)及其制备方法和用途。
背景技术
三核醋酸钯常作为偶联反应最常用的均相催化剂被广泛应用于天然产物、聚合物、功能材料、液晶、药物分子的合成，在这些生产工艺中，含氮化合物被作为助催化剂加入到反应体系中，提高催化剂的催化活性。
张奇龙等用醋酸钯和三乙胺催化合成一种识别硫氰酸根的荧光探针，该反应中，三乙胺即作为溶剂又作为助催化剂；史炳锋等以六氟异丙醇溶剂，醋酸钯为金属催化剂，乙酰基叔亮氨酸为助剂合成大位阻的氨基酸及短肽；刘克印等以冰醋酸为溶剂，醋酸钯和2-(6-氨基-萘基)苯并噻唑混合物为催化剂合成一种检测一氧化碳的金属有机框架材料等等。
上述这些都是在有机溶剂的作用下完成，而现代工业生产的绝大部分也需要在水作溶剂的条件下进行，醋酸钯不溶于水，它的催化活性在这些反应中的活性严重降低。
因此，寻找一种价格低，合成工艺简单，溶于水的钯催化剂也是钯催化剂发展的一个重要方向。
发明内容
本发明涉及一种以助催化剂为配体、溶于水的四核钯催化剂及其制备方法和用途，并应用于催化对2-溴噻吩与对甲氧基苯硼酸之间的偶联反应。
d8电子构型的Pd(Ⅱ)，一般进行dsp2杂化，形成平面化合物。本发明的一种水溶性环状四核钯(II)配合物是以四个(R2CH2COO)Pd片段和R1NH-配体桥联形成钯(Ⅱ)环状配合物，它的结构为：
目前，RCOO-与Pd(Ⅱ)配位可以形成简单的三核羧酸钯[Pd(RCOO)2]3。以助催化剂R1NH-和R2CH2COO-同时配位的四核钯尚未见报道。
为此本发明提供了一种水溶性好的、配体R2CH2COO-和助催化剂R1NH-桥联环状四核钯(Ⅱ)配合物的合成方法，操作工艺简单，目标产物的纯度及产率较高。
本发明以PdCl2为钯源，经过两步反应得到目标配合物，培养的单晶经X-单晶衍射仪等结构测定发现：在OH-、Pd2+和R1NH-共同作用下，作为双齿配体的HCH2COO-同时配位两个Pd2+形成的单元体，R1NH2失去一个H，以R1NH-桥连自组装形成四核钯的八圆环状中性分子。
本发明的制备方法采用的技术方案是：
步骤一：在氮气氛下，将钯源置于三颈圆底烧瓶，加入一定体积3％的胺，50℃下加热搅拌，待溶液变为澄清的淡黄色时，加入含碳酸氢的化合物，生成白色沉淀，冷却，过滤，用冰水洗3次，得到白色固体粉末。
作为优选，所述的含碳酸氢根的化合物为碳酸氢钠、碳酸氢钾、碳酸氢铵或者二氧化碳的溶液；进一步优选为：二氧化碳的溶液。
步骤二：将上述白色粉末加蒸馏水溶解，在冰水浴下加入氢氧化物，剧烈搅拌反应24h。过滤除去不溶物，将滤液转移至1L三颈圆底烧瓶中，在氮氛下，缓缓滴加一定比例的羧酸酐和酰胺的混合物，搅拌，室温下反应48h，得到微有黑色沉淀的无色溶液，过滤，将所得的滤液冷冻干燥8h，得到外观为淡黄粉末的目标产物。
作为优选上述氢氧化物为氢氧化钡或氢氧化钙，进一步优选为氢氧化钡；
作为优选上述羧酸酐和酰胺的混合物比值为0.1～0.9，进一步优选为0.5。
步骤三：将步骤二的淡黄粉末溶于少量去离子水中，采用溶剂扩散法培养单晶。1个月后得到无色透明的针状晶体。
步骤四：以[Pd(CH3COO)2]3为参照物，评价目标化合物对2-溴噻吩与对甲氧基苯硼酸之间偶联反应的催化活性。
通过结构检索，尚未发现与本发明申请相关的公开报道。
附图说明
图1是本发明的[(CH3COO)Pd(NH2)]4·11(H2O)的分子结构图。
图2是本发明的[(CH3COO)Pd(NH2)]4·11(H2O)晶体结构堆积图(CCDC：1908865)。
具体实施方式
实施例1
一种水溶性环状四核钯(Ⅱ)配合物的制备方法(含活性评价方法)，包括以下步骤：
步骤一：在氮气氛下，将PdCl2 1.77g钯源置于三颈圆底烧瓶，加入100mL 3％的氨水溶解，50℃下加热搅拌，待溶液变为澄清的淡黄色时，通入CO2形成饱和溶液同时有大量白色沉淀生成，冷却，过滤，用冰水洗3次，得到白色固体粉末。
步骤二：将上述白色粉末加蒸馏水溶解，在冰水浴下加入Ba(OH)2 3.42g，剧烈搅拌反应24h。过滤除去不溶物，将滤液转移至1L三颈圆底烧瓶中，在氮氛下，缓缓滴加1：1的冰醋酸和乙酰胺的混合物5mL，搅拌，室温下反应48h，过滤除去少量黑色沉淀，得到无色滤液，将滤液冷冻干燥8h，得到外观为淡黄粉末的目标产物8.82g，产率95.46％。
步骤三：将步骤二的目标产物2g溶于20mL去离子水中，采用溶剂扩散法培养单晶。1个月后得到无色透明的针状晶体。
步骤四：催化活性评价
反应条件a：2-溴噻吩(1.0equiv.)，对甲氧基苯硼酸(1.1equiv.)，K2CO3(1.5equiv.)，Pd催化剂(5mol％相对于2-溴噻吩)，在无水THF:H2O＝1:1(10mL)中70℃反应12h。
反应条件b：2-溴噻吩(1.0equiv.)，对甲氧基苯硼酸(1.1equiv.)，K2CO3(1.5equiv.)，Pd催化剂(5mol％相对于2-溴噻吩)，在无水甲苯:H2O＝1:1(10mL)中110℃反应12h。
目标产物的结构测试结果：
1、元素分析：按[(CH3COO)Pd(NH2)]4·11(H2O)的计算值(％)：C，10.39；H，4.54；N，6.13；Pd，45.89。实测值(％)：C，11.70；H，4.85；N，6.13；Pd，45.76。
2、核磁：1H NMR(500MHz,D2O)δ(ppm)：1.802(s,12H)，4.68(s,H2O+8H)，13C NMR(500MHz,D2O)δ(ppm)24.23(s,CH3-)，182.41(m,COO-)。
3、热重分析谱DTA/TG：在242℃吸热峰，失重率40.22％，相当于失去4个NH2 -和4个CH3COO-，剩余金属钯。
4、晶体结构
见附图1。
以上测定结果符合[CH3COO)Pd(NH2)]4·11(H2O)的组成和结构式。
5、催化评价结果
见表1。
表1不同钯催化剂对下述偶联反应的影响
两种钯化合物作为催化剂，在水作为溶剂的条件下，都对2-溴噻吩与对甲氧基苯硼酸的偶联反应都具有催化活性，总体来看[CH3COO)Pd(NH2)]4·11(H2O)的催化活性要略高于参照物，但是产率基本都能够维持在75％以上，且不需要进行N2保护和无水无氧的条件。因此本发明的钯化合物对偶联反应催化剂的选择具有一定的指导意义。
Claims (3)
1.一种水溶性环状四核钯(Ⅱ)配合物，其特征在于，以R2CH2COO-和R1NH-桥连形成环状四核钯(Ⅱ)配合物，结构式如下：
结构式中：R1、R2为氢，n为11。
2.一种根据权利要求1所述的水溶性环状四核钯(Ⅱ)配合物的制备方法，其特征在于，合成过程包括以下步骤：
步骤一：在氮气气氛下，将PdCl2 1.77g置于三颈圆底烧瓶，加入100mL 3％的氨水溶解，50℃下加热搅拌，待溶液变为澄清的淡黄色时，通入CO2形成饱和溶液同时有大量白色沉淀生成，冷却，过滤，用冰水洗3次，得到白色固体粉末；
步骤二：将上述白色粉末加蒸馏水溶解，在冰水浴下加入Ba(OH)2 3.42g，剧烈搅拌反应24h，过滤除去不溶物，将滤液转移至1L三颈圆底烧瓶中，在氮气气氛下，缓缓滴加1:1的冰醋酸和乙酰胺的混合物5mL，搅拌，室温下反应48h，过滤除去少量黑色沉淀，得到无色滤液，将滤液冷冻干燥8h，得到外观为淡黄粉末的目标产物8.82g；
步骤三：将步骤二的目标产物2g溶于20mL去离子水中，采用溶剂扩散法培养单晶，1个月后得到无色透明的针状晶体。
3.一种根据权利要求1所述的水溶性环状四核钯(Ⅱ)配合物的用途，其特征在于：应用于催化对2-溴噻吩与对甲氧基苯硼酸之间的偶联反应中。
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