Solvent-Free “One-Pot” Biginelli Reaction Catalyzed by Mononuclear Cd(II) Complex Containing Benzenesulfonic Acid Ligands

doi:10.6023/A25030096

Abstract

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

Cite this article

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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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

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

	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

	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

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

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