氮杂环卡宾-钯功能化的配位聚合物（NHC-Pd@Zn-L）：合成、表征及催化Suzuki-Miyaura交叉偶联反应

doi:10.11949/0438-1157.20220233

摘要/Abstract

摘要：

以 $1,3$ -二(1-羧乙基)咪唑盐(HL)和Zn(NO₃)₂·6H₂O反应合成二维配位聚合物[Zn(L)₂] _n (Zn-L)，产物再与K₂PdCl₄在四氢呋喃溶液中反应引入氮杂环卡宾-钯（NHC-Pd）催化位点，制得催化剂NHC-Pd@Zn-L，并通过PXRD、TGA、ICP、SEM、EDS和XPS进行表征。结果表明，NHC-Pd@Zn-L具有良好的热稳定性且修饰后晶体的框架结构没有发生变化，Pd以NHC-Pd的形式结合在Zn-L中，并均匀分散在配位聚合物中。将NHC-Pd@Zn-L用于催化Suzuki-Miyaura交叉偶联反应，当以苯硼酸和溴苯为底物，催化剂用量为15 mg，乙醇为溶剂，碳酸钾为碱的条件下60℃反应6 h，产率达到>99%，而且催化剂易于回收并可循环使用3次。

关键词: 氮杂环卡宾-钯, Suzuki-Miyaura交叉偶联反应, 催化, 配位聚合物, 后合成修饰

Abstract:

A two-dimensional coordination polymer [Zn(L)₂] _n_{(Zn-L) was synthesized by the reaction of 1,3-bis(1-carboxyethyl) imidazolium salt (HL) and Zn(NO₃)₂·6H₂O. The product was then reacted with K₂PdCl₄ in tetrahydrofuran solution to introduce nitrogen heterocyclic carbene-palladium (NHC-Pd) catalytic site to prepare the catalyst NHC-Pd@Zn-L, and the structure was characterized by PXRD, TGA, ICP, SEM, EDS and XPS. The results showed that the catalyst had high thermal stability and the framework structure of the modified Zn-L did not change, and Pd was bound in Zn-L in the form of NHC-Pd and uniformly dispersed in the coordination polymer. NHC-Pd@Zn-L was used to catalyze the Suzuki-Miyaura cross-coupling reaction. When phenylboronic acid and bromobenzene were used as substrates, the catalyst dosage was 15 mg, ethanol was used as solvent, and potassium carbonate was used as base for the reaction at 60℃, 6 h, the yield reaches >99%, and the catalyst is easy to recover and can be recycled for 3 times.}

Key words: N-heterocyclic carbine-Pd, Suzuki-Miyaura cross-coupling reaction, catalysis, coordination polymer, post-synthetic modification

中图分类号:

O 611.4

郭杰, 张帆, 谢世玉, 由立新, 孙亚光. 氮杂环卡宾-钯功能化的配位聚合物（NHC-Pd@Zn-L）：合成、表征及催化Suzuki-Miyaura交叉偶联反应[J]. 化工学报, 2022, 73(8): 3608-3614.

Jie GUO, Fan ZHANG, Shiyu XIE, Lixin YOU, Yaguang SUN. NHC-Pd functionalized coordination polymer (NHC-Pd@Zn-L): synthesis, characterization and catalytic performance in Suzuki-Miyaura cross-coupling reaction[J]. CIESC Journal, 2022, 73(8): 3608-3614.

图/表 11

图1 NHC-Pd@Zn-L的合成路线

Fig.1 Synthetic route of NHC-Pd@Zn-L

图2 联苯标准曲线

Fig.2 Standard curve of biphenyl yield

图3 样品的粉末X射线衍射分析

Fig.3 PXRD patterns of the samples

图4 Zn-L与NHC-Pd@Zn-L的热重分析

Fig.4 Thermogravimetric analysis of Zn-L and NHC-Pd@Zn-L

图5 NHC-Pd@Zn-L的XPS谱图（a）；反应前后NHC-Pd@Zn-L中Pd的XPS谱图（b）

Fig.5 XPS spectrum of NHC-Pd@Zn-L (a); XPS spectra of Pd in NHC-Pd@Zn-L before and after reactions (b)

图6 NHC-Pd@Zn-L的SEM图和元素谱图

Fig.6 SEM image of NHC-Pd@Zn-L and atoms in the elemental map

图7 NHC-Pd@Zn-L催化反应后的TEM图

Fig.7 TEM image of NHC-Pd@Zn-L catalytic reaction

图8 NHC-Pd@Zn-L的EDS谱图

Fig.8 EDS spectrum of NHC-Pd@Zn-L

表1 NHC-Pd@Zn-L催化溴苯与苯硼酸的Suzuki-Miyaura交叉偶联反应条件的优化

Table 1 Optimization of conditions for the Suzuki-Miyaura cross-coupling reaction of bromobenzene and phenylboronic acid catalyzed by NHC-Pd@Zn-L

序号	溶剂	碱	时间/h	催化剂/mg	温度/℃	产率/%
1	DMF	K₂CO₃	6	15	60	32
2	toluene	K₂CO₃	6	15	60	21
3	H₂O	K₂CO₃	6	15	60	60
4	EtOH	K₂CO₃	6	15	60	>99
5	EtOH	Cs₂CO₃	6	15	60	95
6	EtOH	NaOH	6	15	60	95
7	EtOH	Et₃N	6	15	60	35
8	EtOH	t-C₄H₉ONa	6	15	60	44
9	EtOH	K₂CO₃	6	10	60	95
10	EtOH	K₂CO₃	6	15	80	93
11	EtOH	K₂CO₃	2	15	60	90
12^①	EtOH	K₂CO₃	6	15	60	99
13^②	EtOH	K₂CO₃	6	15	60	84

表2 NHC-Pd@Zn-L催化的芳基卤化物与芳基硼酸的Suzuki-Miyaura交叉偶联反应

Table 2 Suzuki-Miyaura cross-coupling reaction of aryl halides and arylboronic acids catalyzed by NHC-Pd@Zn-L

序号	芳基卤化物	芳基硼酸	产物	产率/ %
1	Ph-Br	Ph-(OH)₂	Ph-Ph	>99
2	Ph-I	Ph-(OH)₂	Ph-Ph	99
3	Ph-Br	p-CH₃-Ph-(OH)₂	p-CH₃-Ph-Ph	98
4	Ph-Br	p-CH₃CO-Ph-(OH)₂	p-CH₃CO-Ph-Ph	95
5	p-CH₃CO-Ph-Cl	Ph-(OH)₂	p-CH₃CO-Ph-Ph	11

表3 NHC-Pd@Zn-L与其他Pd负载配位聚合物在芳基卤苯与苯硼酸反应中最优催化活性的比较

Table 3 Comparison of the optimal catalytic activities of NHC-Pd@Zn-L and other Pd-supported coordination polymers in the reaction of aryl halobenzene with phenylboronic acid

序号	催化剂	反应条件	产率/%	文献
1	NHC-Pd@Zn-L	60℃，6 h	>99	本文
2	[SmPd₂[L]₂Cl₄] _n [H₃O] _n	80℃, 6 h	99	[8]
3	Pd@Eu-MOF	80℃, 6 h	>99	[11]
4	Pd(0)@1a	60℃，24 h	>99	[12]
5	Fe₃O₄@La-MOF-Schiff-Pd/Ni	80℃, 6 h	95	[13]
6	Pd@ZIF-92	80℃, 6 h	>99	[22]
7	MOF-253·0.05PdCl₂	100℃, 8 h	98	[23]
8	MOP-BPY(Pd)	80℃, 12 h	99	[31]
9	Pd NPs at NHC at ZIF-8	90℃, 0.25 h	99	[32]
10	Pd-NHC-MIL-101(Cr)	90℃, 0.17 h	96	[33]
11	Pd-HoMOF	100℃, 1 h	>99	[34]
12	Pd NCs	75℃, 10 h	96	[35]
13	m-6,6′-Me₂bpy-MOF-Pd	85℃, 12 h	74	[36]
14	m-6,6′-Me₂bpy-MOF-PdCl₂	85℃, 12 h	99	[37]
15	UiO-66-Pyta-Pd	80℃, 2 h	80	[38]

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