Synthesis, Crystal Structure and Homogeneous Catalytic Performance of Zinc Complex Based on Diethylenetriamine Ligand†

doi:10.7503/cjcu20141142

Abstract

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

CLC Number:

O614
O643

TrendMD:

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

Figures/Tables 12

References 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)