含苯磺酸类配体的单核Cd(II)配合物催化无溶剂“一锅法”Biginelli反应

doi:10.6023/A25030096

摘要/Abstract

以对硝基甲苯邻磺酸根(C₇H₆NO₅S^－, HL^－)和4,4'-联吡啶(bpy)为主辅配体, 利用溶剂热合成法制备了结构新颖的单核镉配合物Cd(C₁₀H₈N₂)₄(C₇H₆NO₅S)₂[简写为Cd(bpy)₄(HL)₂], 并采用X射线单晶衍射、扫描电镜、能量色散光谱、氮气吸附/脱附分析和热重分析对其进行了表征. 以Biginelli反应为模版, 探究了Cd(bpy)₄(HL)₂的催化性能, 实验结果表明, Cd(bpy)₄(HL)₂在催化Biginelli反应中性能良好, 在无溶剂、90 ℃条件下, 芳香醛、芳香酮和脲通过三组分“一锅法”生成了一系列4,6-二芳基-3,4-二氢嘧啶-2(1H)-酮, 反应时间短, 产物产率高, 催化剂通过简单的相分离便可实现回收及重复使用, 即使连续催化6次, 催化剂仍保持较高的催化活性. 利用密度泛函理论(DFT)对Cd(bpy)₄(HL)₂和反应物进行了结构优化, 通过分析Cd(bpy)₄(HL)₂的Mulliken电荷、分子表面静电势(ESP)和平均局部离子化能(ALIE)预测了配合物的活性位点; 通过分析苯甲醛、苯乙酮和脲的ESP预测了反应物的反应位点; 并利用X射线光电子能谱对活化作用进行了验证, 从而推测出可能的催化机理. Cd(bpy)₄(HL)₂具有的结构特点使其在催化反应中易于与反应底物接触, 所具有双活性位点使其在催化反应中呈现共催化作用, 从而促进反应的进行.

关键词: 苯磺酸配合物, Biginelli反应, 催化活性, 密度泛函理论, 催化机理

In this work, a structural novel mononuclear cadmium complex, Cd(C₁₀H₈N₂)₄(C₇H₆NO₅S)₂ [abbreviated as Cd(bpy)₄(HL)₂], was synthesized by solvothermal method using 4-nitrotoluene-2-sulfonate anion (C₇H₆NO₅S^－, HL^－) and 4,4'-bipyridine (bpy) as the main and auxiliary ligands. The complex was characterized by X-ray single crystal diffraction, scanning electron microscopy, energy dispersive spectroscopy, nitrogen adsorption/desorption analysis and thermogravimetric analysis. The catalytic performance of Cd(bpy)₄(HL)₂ was investigated by using the Biginelli reaction as a model. The experimental results showed that Cd(bpy)₄(HL)₂ exhibited excellent catalytic performance in the Biginelli reaction. A series of 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-ones were synthesized from aromatic aldehydes, aromatic ketones and urea through a three-component one-pot method under solvent-free and 90 ℃ conditions. The reaction time was short, the product yields were high, and the catalyst could be recovered and reused by simple phase separation. Even after six consecutive catalytic cycles, the catalyst still maintained high catalytic activity. The catalysts before and after catalysis were characterized by powder X-ray diffraction, infrared spectroscopy and X-ray photoelectron spectroscopy, and the test findings were compared. From the results, the phase purity, composition and structure of the catalyst did not change significantly after continuous use for six times, and the chemical properties of the catalyst were stable. The structures of Cd(bpy)₄(HL)₂ and the reactants were optimized by density functional theory (DFT). The active sites of the complex were predicted by analyzing the Mulliken charges, molecular surface electrostatic potential (ESP) and average local ionization energy (ALIE) of Cd(bpy)₄(HL)₂. The reaction sites of the reactants were predicted by analyzing the ESP of benzaldehyde, acetophenone and urea. The activation effect of the active sites on the reaction sites was verified by X-ray photoelectron spectroscopy. Therefore, the possible catalytic mechanism was speculated. The structural characteristic of Cd(bpy)₄(HL)₂ makes it easy to contact with the reaction substrates, and the presence of two active sites enables it to exhibit co-catalytic effect in the catalytic reaction, thereby promoting the reaction.

Key words: benzenesulfonic acid complex, Biginelli reaction, catalytic activity, density functional theory, catalytic mechanism

引用此文

王鑫, 史燚威, 杨瑞杰, 宋志国, 王敏. 含苯磺酸类配体的单核Cd(II)配合物催化无溶剂“一锅法”Biginelli反应[J]. 化学学报, 2025, 83(7): 674-684.

Xin Wang, Yiwei Shi, Ruijie Yang, Zhiguo Song, Min Wang. Solvent-Free “One-Pot” Biginelli Reaction Catalyzed by Mononuclear Cd(II) Complex Containing Benzenesulfonic Acid Ligands[J]. Acta Chimica Sinica, 2025, 83(7): 674-684.

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图/表 17

Parameter		Value
Formula		C₃₄CdN₆O₁₀S₂
Formula weight		828.92
Crystal system		Monoclinic
Space group		P2₁/n
a/nm		0.89086(3)
b/nm		1.61511(5)
c/nm		1.27040(4)
α/(°)		90
β/°		103.7390(10)
γ/°		90
V/nm³		1.77560(10)
Z		2
Dc/(mg•m^－3)		1.550
Goodness-of-fit F²		1.113
R₁, ωR₂		0.0338, 0.0986
R₁, ωR₂ (all data)		0.0366, 0.1019

表1. Cd(bpy)4(HL)2的晶体学数据a,b

Table 1. Crystallographic data for Cd(bpy)4(HL)2

	Bond length/nm			Bond angle/(°)
	X-ray	B3LYP		X-ray	B3LYP
Cd(1)—O(1)#1	0.2300(2)	0.2363	O(1)#1—Cd(1)—O(1)	180.0	179.35
Cd(1)—O(1)	0.2300(2)	0.2363	N(1)#1—Cd(1)—N(1)	180.0	179.69
Cd(1)—N(1)	0.2315(2)	0.2378	N(2)#1—Cd(1)—N(2)	180.0	179.44
Cd(1)—N(1)#1	0.2315(2)	0.2378	O(1)#1—Cd(1)—N(2)#1	85.24(9)	86.93
Cd(1)—N(2)	0.2411(2)	0.2457	O(1)#1—Cd(1)—N(1)	90.32(9)	92.80
Cd(1)—N(2)#1	0.2411(2)	0.2457	N(1)—Cd(1)—N(2)#1	88.20(9)	89.16

表2. Cd(bpy)4(HL)2的部分键长(nm)和键角(°)的实验值和计算值a

Table 2. Partial bond length (nm) and bond angle (°) of Cd(bpy)4(HL)2

图1. Cd(bpy)4(HL)2的(a)晶体结构、(b)二维网状结构和(c)三维网状结构

Figure 1. (a) Crystal structure, (b) two-dimensional network structure and (c) three-dimensional network structure of Cd(bpy)4(HL)2

图2. (a~d) Cd(bpy)4(HL)2的SEM图像, (e) Cd(bpy)4(HL)2的EDS及(f~k) Cd(bpy)4(HL)2中Cd, C, N, S, O的元素映射

Figure 2. (a~d) SEM images of Cd(bpy)4(HL)2, (e) EDS, and (f~k) elemental mappings of Cd, C, N, S, O of Cd(bpy)4(HL)2

图3. Cd(bpy)4(HL)2的(a) N2吸附-脱附等温线和(b) BJH孔径分布图

Figure 3. (a) N2 adsorption-desorption isotherm and (b) BJH pore size distribution of Cd(bpy)4(HL)2

图4. Cd(bpy)4(HL)2的热重曲线图

Figure 4. TG curves of Cd(bpy)4(HL)2

图式1. Cd(bpy)4(HL)2催化合成4,6-二芳基-3,4-二氢嘧啶-2(1H)-酮

Scheme 1. Synthesis of 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-ones catalyzed by Cd(bpy)4(HL)2

Entry	n_benzaldehyde∶ n_acetophenone∶n_urea	Temp./ ℃	Catal. amount/ mmol	Time/min	Yield/%
1	1.0∶1.0∶1.0	90	0.3	46	74.6
2	1.0∶1.0∶1.1	90	0.3	16	88.2
3	1.0∶1.0∶1.2	90	0.3	29	84.2
4	1.0∶1.0∶1.3	90	0.3	37	82.8
5	1.0∶1.0∶1.1	50	0.3	41	67.6
6	1.0∶1.0∶1.1	70	0.3	28	80.7
7	1.0∶1.0∶1.1	110	0.3	20	84.4
8	1.0∶1.0∶1.1	90	0.1	18	83.3
9	1.0∶1.0∶1.1	90	0.2	18	84.3
10	1.0∶1.0∶1.1	90	0.4	16	86.2
11	1.0∶1.0∶1.1	90	0.5	16	86.1

表3. 原料配比、反应温度和Cd(bpy)4(HL)2用量优化

Table 3. Optimization of raw material ratio, reaction temperature and the amount of Cd(bpy)4(HL)2

表4. Cd(bpy)4(HL)2催化合成4,6-二芳基-3,4-二氢嘧啶-2(1H)-酮a

Table 4. Synthesis of 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-ones catalyzed by Cd(bpy)4(HL)2

图5. 不同芳香醛上羰基碳的Mulliken电荷和芳香醛的分子直径

Figure 5. Mulliken charges of carbonyl carbon on different aromatic aldehydes and molecular diameters of aromatic aldehydes

图6. (a) Cd(bpy)4(HL)2的重复使用情况以及Cd(bpy)4(HL)2催化6次前后的(b)粉末X射线衍射图、(c)红外光谱图、(d) X射线光电子能谱总谱和(e~i) Cd3/2d, C1s, O1s, N1s和S2p的X射线光电子能谱

Figure 6. (a) Reuse of Cd(bpy)4(HL)2, and (b) powder X-ray diffraction pattern, (c) infrared spectra, XPS spectra of (d) total spectrum and (e~i) Cd3/2d, C1s, O1s, N1s and S2p of Cd(bpy)4(HL)2 before and after six catalytic times

Entry	Catalyst (n_catalyst∶n_benzaldehyde)	Raw material ratio^a	Condition	Time/min	Yield/%	Ref.
1	NiFe₂O₄@SiO₂ⁿPr@glucose amine (10%)	1.0∶1.0∶1.0	25 ℃ (H₂O)	120	90.0	[39]
2	Ƴ-Fe₂O₃-SO₃H (5%)	1.0∶1.0∶1.5	80 ℃ (solvent free)	100	90.0	[40]
3	[TSPi][CF₃SO₃]₂ (2.5%)	1.0∶1.0∶1.2	r.t. (CH₂Cl₂, grind)	16	89.0	[41]
4	PPh₃ (20%)/I₂ (15%)	1.2∶1.0∶1.5	80 ℃ (1,4-dioxane)	120	82.0	[42]
5	LDA (20%)	1.2∶1.5∶1.5	0 ℃ (THF)	60	81.0	[43]
6	Cd(bpy)₄(HL)₂ (3%)	1.0∶1.0∶1.1	90 ℃ (solvent free)	16	88.2	This work

表5. 催化剂比较

Table 5. Comparison of catalysts

图7. Cd(bpy)4(HL)2的优化分子模型

Figure 7. Optimized molecular model of Cd(bpy)4(HL)2

Atom	Charge/eV	Atom	Charge/eV	Atom	Charge/eV	Atom	Charge/eV
Cd(1)	25.80	C(11)	0.74	N(79)	－9.71	H(106)	4.14
C(2)	1.77	C(12)	－3.27	O(83)	－14.61	H(107)	5.28
C(3)	1.82	C(13)	－3.27	O(86)	－16.98	C(118)	－13.63
C(4)	－3.89	C(14)	－0.19	O(87)	－16.95	H(119)	5.20
H(5)	5.82	H(15)	3.92	C(99)	－9.80	H(121)	3.95
C(6)	－3.92	C(16)	0.19	C(100)	－2.29	H(120)	5.77
H(7)	6.01	H(17)	4.19	C(101)	4.41	N(109)	1.42
C(8)	0.93	H(18)	4.11	C(102)	8.38	O(112)	－7.84
H(9)	－4.03	H(19)	4.19	H(103)	6.67	O(113)	－7.76
H(10)	4.38	N(78)	－14.59	C(104)	－4.68	C(105)	－2.34

表6. Cd(bpy)4(HL)2部分原子的Mulliken电荷

Table 6. Mulliken charge of Cd(bpy)4(HL)2 part atom

图8. Cd(bpy)4(HL)2的(a)表面静电势填色图、(b)表面平均局部离子化能填色图及(c~e)苯甲醛、苯乙酮和脲的表面静电势填色图

Figure 8. (a) Surface electrostatic potential coloring diagram, (b) surface average local ionization energy coloring diagram of Cd(bpy)4(HL)2, and (c~e) Surface electrostatic potential coloring diagram of benzaldehyde, acetophenone and urea

图9. 不同反应时间催化体系的(a) Cd3/2d, (b) O1s和(c) N1s的XPS谱图

Figure 9. XPS spectra of (a) Cd3/2d, (b) O1s, and (c) N1s in catalytic systems with different reaction times

图10. 可能的催化机理

. Possible catalytic mechanism

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