基于二乙烯三胺配体的锌配合物的合成、晶体结构及均相催化性能

doi:10.7503/cjcu20141142

摘要/Abstract

摘要：

以二乙烯三胺(DETA)为配体合成了1个五配位的锌配合物[Zn(OAc)₂(DETA)]·H₂O, 通过元素分析、红外光谱和X射线单晶衍射对其结构进行了表征, 并研究了其催化Henry反应的性能和机理. 结果表明, 配合物属于单斜晶系, P2₁/c空间群, 中心锌原子与配体的3个氮原子及2个羧基氧原子配位, 形成扭曲的三角双锥构型; 通过分子内和分子间的氢键作用, 配合物分子进一步形成三维晶体结构; 在优化条件下, 配合物对Henry反应有良好的催化性能, 不同醛反应底物在Henry反应方面具有一定普适性.

关键词: 二乙烯三胺, 锌配合物, 晶体结构, 催化性能, Henry反应

Abstract:

Using diethylenetriamine(DETA) as ligand, a five-coordinated zinc complex [Zn(OAc)₂·(DETA)]·H₂O was synthesized. The structure of the complex was characterized by elemental analysis, infrared spectroscopy(IR) and X-ray single crystal diffraction(XRD), and the catalytic performance and the mechanism in catalyzing Henry reaction were studied. The results show that the complex belongs to monoclinic crystal system, space group P2₁/c. The central zinc atom is coordinated with three nitrogen atoms and two oxygen atoms, forming a distorted triangular bipyramidal configuration, then a three-dimensional crystal structure is further formed through intramolecular and intermolecular hydrogen bonds. In the optimized conditions, the complex plays a good catalytic performance upon Henry reaction, and the reaction substrates of different aldehydes are universal to a certain extent.

Key words: Diethylenetriamine, Zinc complex, Crystal structure, Catalytic performance, Henry reaction

中图分类号:

O614
O643

TrendMD:

刘超, 卓馨, 成慧, 刘闯, 刘新华. 基于二乙烯三胺配体的锌配合物的合成、晶体结构及均相催化性能. 高等学校化学学报, 2015, 36(5): 831.

LIU Chao, ZHUO Xin, CHENG Hui, LIU Chuang, LIU Xinhua. Synthesis, Crystal Structure and Homogeneous Catalytic Performance of Zinc Complex Based on Diethylenetriamine Ligand^†. Chem. J. Chinese Universities, 2015, 36(5): 831.

图/表 12

参考文献 28

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Empirical formula	C₈H₂₁N₃O₅Zn	Z	4
Formula weight	304.65	D_c/(g·cm^-3)	1.453
Crystal system	Monoclinic	μ/mm^-1	1.777
Space group	P2₁/c	F(000)	640
Temperature/K	296(2)	Reflections collected/unique(R_int)	7896/2593(0.029)
a/nm	1.2433(7)	Data/restraints/parameters	2593/0/156
b/nm	1.3378(7)	Goodness-of-fit on F²	1.085
c/nm	0.8676(5)	Final R indices[I>2σ(I)]	R₁=0.0274, wR₂=0.0696
β/(°)	105.213(8)	R indices(all data)	R₁=0.0320, wR₂=0.0725
Volume/nm³	1.3924(13)

Empirical formula	C₈H₂₁N₃O₅Zn	Z	4
Formula weight	304.65	D_c/(g·cm^-3)	1.453
Crystal system	Monoclinic	μ/mm^-1	1.777
Space group	P2₁/c	F(000)	640
Temperature/K	296(2)	Reflections collected/unique(R_int)	7896/2593(0.029)
a/nm	1.2433(7)	Data/restraints/parameters	2593/0/156
b/nm	1.3378(7)	Goodness-of-fit on F²	1.085
c/nm	0.8676(5)	Final R indices[I>2σ(I)]	R₁=0.0274, wR₂=0.0696
β/(°)	105.213(8)	R indices(all data)	R₁=0.0320, wR₂=0.0725
Volume/nm³	1.3924(13)

Compound	¹H NMR(400 MHz, CDCl₃)
2	7.40-7.33(m, 5H, Ar-H), 5.41(dd, J=3.2, 9.6 Hz, 1H, ArCH), 4.56(dd, J=9.6, 13.2 Hz, 1H, CH₂), 4.47(dd, J=3.2, 13.2 Hz, 1H, CH₂), 3.04(br, 1H, OH)
3	7.28-7.21(m, 4H, Ar-H), 5.41(dd, J=2.8, 9.6 Hz, 1H, ArCH), 4.57(dd, J=9.6, 13.2 Hz, 1H, CH₂), 4.47(dd, J=2.8, 13.2 Hz, 1H, CH₂), 2.88(br, 1H, OH), 2.37(s, 3H, CH₃)
4	7.52-7.17(m, 4H, Ar-H), 5.63(dd, J=2.4, 9.7 Hz, 1H, ArCH), 4.52(dd, J=9.7, 13.3 Hz, 1H, CH₂), 4.41(dd, J=2.4, 13.3 Hz, 1H, CH₂), 2.93(br, 1H, OH), 2.38(s, 3H, CH₃)
5	7.38-7.28(m, 4H, Ar-H), 5.45(dd, J=9.6, 3.2 Hz, 1H, ArCH), 4.56(dd, 1H, J=9.6, 13.6 Hz, 1H, CH₂), 4.48(dd, 1H, J=3.2, 13.6 Hz, 1H, CH₂), 3.05(br, 1H, OH)
6	7.64-7.32(m, 4H, Ar-H), 5.75(dd, 1H, J=2.4, 9.6 Hz, 1H, ArCH), 4.59(dd, J=9.6, 13.5 Hz, 1H, CH₂), 4.35(dd, J=2.4, 13.5 Hz, 1H, CH₂), 3.03(br, 1H, OH)
7	8.28-7.63(m, 4H, Ar-H ), 5.60(dd, J=3.2, 8.0 Hz, 1H, ArCH), 4.61(dd, J=8.0, 13.6 Hz, 1H, CH₂), 4.57(dd, J=3.2, 13.6 Hz, 1H, CH₂), 3.23(br, 1H, OH)
8	8.07-7.52(m, 4H, Ar-H), 6.03(dd, J=3.2, 9.6 Hz, 1H, ArCH), 4.82(dd, J=9.2, 13.6 Hz, 1H, CH₂), 4.53(dd, J=2.4, 13.6 Hz, 1H, CH₂), 3.36(br, 1H, OH)
9	4.40(dd, J=3.6, 7.6 Hz, 1H, ArCH), 4.36(dd, J=7.6, 13.2 Hz, 1H, CH₂), 4.31(dd, J=3.6, 13.2 Hz, 1H, CH₂), 2.60(br, 1H, OH), 1.63-1.27(m, 4H, CH₂CH₂), 0.98-0.93(t, 3H, CH₃)
10	4.50(dd, J=8.9, 13.1 Hz, 1H, CH₂NO₂), 4.42(dd, J=3.0, 13.1 Hz, 1H, CH₂NO₂), 4.12-4.08[m, 1H, CH(OH)], 2.52(br, 1H, OH), 1.84-1.06(m, 11H, cHex-H)
11	7.41-6.38(m, 3H, Furan-H), 5.44(dd, J=3.6, 9.2 Hz, 1H, Furan-CH), 4.78(dd, J=9.2, 13.6 Hz, 1H, CH₂), 4.67(dd, J=3.6, 13.6 Hz, 1H, CH₂), 3.19(br, 1H, OH)
12	8.55-7.26(m, 4H, Py-H), 5.48(dd, J=3.4, 9.6 Hz, 1H, Py-CH), 4.78(dd, J=9.6, 13.2 Hz, 1H, CH₂), 4.64(dd, J=3.4, 13.2 Hz, 1H, CH₂), 3.56(br, 1H, OH)

Compound	¹H NMR(400 MHz, CDCl₃)
2	7.40-7.33(m, 5H, Ar-H), 5.41(dd, J=3.2, 9.6 Hz, 1H, ArCH), 4.56(dd, J=9.6, 13.2 Hz, 1H, CH₂), 4.47(dd, J=3.2, 13.2 Hz, 1H, CH₂), 3.04(br, 1H, OH)
3	7.28-7.21(m, 4H, Ar-H), 5.41(dd, J=2.8, 9.6 Hz, 1H, ArCH), 4.57(dd, J=9.6, 13.2 Hz, 1H, CH₂), 4.47(dd, J=2.8, 13.2 Hz, 1H, CH₂), 2.88(br, 1H, OH), 2.37(s, 3H, CH₃)
4	7.52-7.17(m, 4H, Ar-H), 5.63(dd, J=2.4, 9.7 Hz, 1H, ArCH), 4.52(dd, J=9.7, 13.3 Hz, 1H, CH₂), 4.41(dd, J=2.4, 13.3 Hz, 1H, CH₂), 2.93(br, 1H, OH), 2.38(s, 3H, CH₃)
5	7.38-7.28(m, 4H, Ar-H), 5.45(dd, J=9.6, 3.2 Hz, 1H, ArCH), 4.56(dd, 1H, J=9.6, 13.6 Hz, 1H, CH₂), 4.48(dd, 1H, J=3.2, 13.6 Hz, 1H, CH₂), 3.05(br, 1H, OH)
6	7.64-7.32(m, 4H, Ar-H), 5.75(dd, 1H, J=2.4, 9.6 Hz, 1H, ArCH), 4.59(dd, J=9.6, 13.5 Hz, 1H, CH₂), 4.35(dd, J=2.4, 13.5 Hz, 1H, CH₂), 3.03(br, 1H, OH)
7	8.28-7.63(m, 4H, Ar-H ), 5.60(dd, J=3.2, 8.0 Hz, 1H, ArCH), 4.61(dd, J=8.0, 13.6 Hz, 1H, CH₂), 4.57(dd, J=3.2, 13.6 Hz, 1H, CH₂), 3.23(br, 1H, OH)
8	8.07-7.52(m, 4H, Ar-H), 6.03(dd, J=3.2, 9.6 Hz, 1H, ArCH), 4.82(dd, J=9.2, 13.6 Hz, 1H, CH₂), 4.53(dd, J=2.4, 13.6 Hz, 1H, CH₂), 3.36(br, 1H, OH)
9	4.40(dd, J=3.6, 7.6 Hz, 1H, ArCH), 4.36(dd, J=7.6, 13.2 Hz, 1H, CH₂), 4.31(dd, J=3.6, 13.2 Hz, 1H, CH₂), 2.60(br, 1H, OH), 1.63-1.27(m, 4H, CH₂CH₂), 0.98-0.93(t, 3H, CH₃)
10	4.50(dd, J=8.9, 13.1 Hz, 1H, CH₂NO₂), 4.42(dd, J=3.0, 13.1 Hz, 1H, CH₂NO₂), 4.12-4.08[m, 1H, CH(OH)], 2.52(br, 1H, OH), 1.84-1.06(m, 11H, cHex-H)
11	7.41-6.38(m, 3H, Furan-H), 5.44(dd, J=3.6, 9.2 Hz, 1H, Furan-CH), 4.78(dd, J=9.2, 13.6 Hz, 1H, CH₂), 4.67(dd, J=3.6, 13.6 Hz, 1H, CH₂), 3.19(br, 1H, OH)
12	8.55-7.26(m, 4H, Py-H), 5.48(dd, J=3.4, 9.6 Hz, 1H, Py-CH), 4.78(dd, J=9.6, 13.2 Hz, 1H, CH₂), 4.64(dd, J=3.4, 13.2 Hz, 1H, CH₂), 3.56(br, 1H, OH)

Zn1-O1	0.2072(2)	Zn1-O3	0.2001(2)	Zn1-N1	0.2157(2)
Zn1-N2	0.2136(2)	Zn1-N3	0.2177(2)	O1-C5	0.1268(3)
O2-C5	0.1239(3)	O3-C7	0.1276(3)	O4-C7	0.1215(3)
O1-Zn1-O3	99.14(7)	O1-Zn1-N1	90.98(7)	O1-Zn1-N2	137.95(6)
O1-Zn1-N3	95.19(8)	O3-Zn1-N1	101.15(7)	O3-Zn1-N2	122.90(7)
O3-Zn1-N3	99.27(8)	N1-Zn1-N2	80.88(6)	N1-Zn1-N3	157.43(8)
N2-Zn1-N3	80.01(7)