密度泛函理论方法研究第一系列过渡金属对甘氨酸的配位能力

doi:10.13232/j.cnki.jnju.2019.06.016

南京大学学报(自然科学版) ›› 2019, Vol. 55 ›› Issue (6): 1040–1046.doi: 10.13232/j.cnki.jnju.2019.06.016

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密度泛函理论方法研究第一系列过渡金属对甘氨酸的配位能力

郭小松,赵红丽,贾俊芳,杨静,孟祥军()

唐山师范学院化学系，唐山，063000

收稿日期:2019-05-05 出版日期:2019-11-30 发布日期:2019-11-29
通讯作者: 孟祥军 E-mail:xjmeng_1974@126.com
基金资助:
河北省高等学校科学技术研究项目(Z2019007);唐山师范学院科学研究项目(2017B01)

Density functional theory study on coordination ability of glycineand the first series transition metals

Xiaosong Guo,Hongli Zhao,Junfang Jia,Jing Yang,XiangJun Meng()

Department of Chemistry, Tangshan Normal University, Tangshan, 063000, China

Received:2019-05-05 Online:2019-11-30 Published:2019-11-29
Contact: XiangJun Meng E-mail:xjmeng_1974@126.com

摘要/Abstract

摘要：

采用密度泛函理论的B3LYP方法，在6?31++G(d,p)基组水平研究第一系列过渡金属二价离子对甘氨酸的配位能力，在M06/6?311+G(d,p)水平上计算构型单点能量与前者对照.每种金属离子配合物的最稳定构型中甘氨酸以羧基的两个O原子配位.金属离子对甘氨酸的配位能力由大到小的次序为Cu²⁺>Ni²⁺> Co²⁺>Zn²⁺>Cr²⁺> Fe²⁺>V²⁺>Mn²⁺>Ti²⁺>Sc²⁺；结合能最大达到-1012.1 kJ·mol^-1.每种构型中轨道相互作用能与静电相互作用能所占比率在50%左右(相差不多)，色散作用仅为0.2%.轨道作用能越大的构型，电子转移数越多.

关键词: 甘氨酸, 金属配合物, 稳定性, 能量分解

Abstract:

B3LYP/6?31++G(d,p) and M06/6?311+G(d,p) methods were applied to investigate the coordination ability of glycine and the first series transition metals. In the most stable structure of every kind metal complex,coordination atoms from glycine are the two oxygen atoms. The order of coordination ability of each metal from big to small is as follows: Cu²⁺>Ni²⁺> Co²⁺>Zn²⁺>Cr²⁺> Fe²⁺>V²⁺>Mn²⁺>Ti²⁺>Sc²⁺,and binding energy of the most stable complex is -1012.1 kJ?mol^-1. In each structure,the rate of orbital interaction energy and electrostatic energy is close to 50% respectively,The dispersion energy is only 0.2%. The more orbital interaction energy ,the more the number of electrons transferred.

Key words: glycine, metal complexes, stability, energy decomposition

中图分类号:

O641

郭小松,赵红丽,贾俊芳,杨静,孟祥军. 密度泛函理论方法研究第一系列过渡金属对甘氨酸的配位能力[J]. 南京大学学报(自然科学版), 2019, 55(6): 1040–1046.

Xiaosong Guo,Hongli Zhao,Junfang Jia,Jing Yang,XiangJun Meng. Density functional theory study on coordination ability of glycineand the first series transition metals[J]. Journal of Nanjing University(Natural Sciences), 2019, 55(6): 1040–1046.

图/表 5

图1

表1

构型[M(Gly1)]2+和[M(Gly2)]2+中的配位键键长数据(单位：pm)"

M		Sc	Ti	V	Cr	Mn	Fe	Co	Ni	Cu	Zn
[M(Gly1)]²⁺	$R M - O 3$	208.9	205.1	199.0	196.8	202.5	198.2	195.0	191.7	194.0	198.1
[M(Gly1)]²⁺	$R M - O 4$	214.7	210.0	202.7	200.8	208.8	204.0	200.1	195.8	198.8	203.9
[M(Gly2)]²⁺	$R M - O 4$	203.6	200.0	195.3	191.4	197.6	190.7	187.9	187.3	186.6	192.2
[M(Gly2)]²⁺	$R M - N 5$	233.3	224.1	216.0	210.2	216.4	210.9	205.2	201.8	197.9	202.5

表1

表2

表3

表4

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[M(Gly1)]²⁺	ΔE _b ¹(kJ·mol^-1)		ΔΔE _b ^2-1(kJ·mol^-1)		ΔΔE _b ^3-1(kJ·mol^-1)
[M(Gly1)]²⁺	B3LYP	M06	B3LYP	M06	B3LYP	M06
[Sc(Gly1)]²⁺	-625.4	-595.2	47.8	37.3	67.1	57.4
[Ti(Gly1)]²⁺	-679.5	-656.8	54.9	46.5	75.5	66.2
[V(Gly1)]²⁺	-743.6	-672.1	28.9	9.9	50.2	32.2
[Cr(Gly1)]²⁺	-801.8	-763.2	31.7	20.4	53.3	43.3
[Mn(Gly1)]²⁺	-719.2	-674.8	32.0	20.4	54.7	44.3
[Fe(Gly1)]²⁺	-771.4	-737.8	-1.7	-8.6	20.2	14.4
[Co(Gly1)]²⁺	-884.7	-825.6	55.8	20.7	48.1	53.5
[Ni(Gly1)]²⁺	-927.3	-849.2	31.0	-7.6	54.3	17.1
[Cu(Gly1)]²⁺	-1012.1	-970.1	24.5	16.3	48.1	41.3
[Zn(Gly1)]²⁺	-863.2	-818.5	4.7	-7.2	31.2	20.3

[M(Gly1)]²⁺	ΔE _inter	ΔE _orb	ΔE _ex	ΔE _els	ΔE _disp	ΔE _deform	ΔQ
[Sc(Gly1)]²⁺	-774.2	-424.4(50.7%)	63.2	-410.9(49.1%)	-2.1(0.2%)	148.8	0.28
[Ti(Gly1)]²⁺	-834.9	-458.5(50.3%)	76.5	-450.7(49.5%)	-2.2(0.2%)	155.4	0.31
[V(Gly1)]²⁺	-906.0	-559.5(56.2%)	89.4	-433.6(43.6%)	-2.3(0.2%)	162.4	0.39
[Cr(Gly1)]²⁺	-982.7	-608.8(57.1%)	83.8	-455.4(42.7%)	-2.3(0.2%)	180.9	0.43
[Mn(Gly1)]²⁺	-888.7	-450.2(46.4%)	81.5	-517.7(53.4%)	-2.3(0.2%)	169.5	0.30
[Fe(Gly1)]²⁺	-968.6	-515.0(48.4%)	95.3	-546.6(51.4%)	-2.3(0.2%)	197.2	0.36
[Co(Gly1)]²⁺	-1017.1	-563.6(51.2%)	83.4	-534.7(48.6%)	-2.2(0.2%)	132.4	0.43
[Ni(Gly1)]²⁺	-1123.9	-668.3(54.8%)	95.3	-548.6(45.0%)	-2.3(0.2%)	196.6	0.52
[Cu(Gly1)]²⁺	-1208.1	-707.6(54.9%)	80.9	-579.2(44.9%)	-2.2(0.2%)	196.0	0.64
[Zn(Gly1)]²⁺	-1029.3	-512.7(47.0%)	62.1	-576.5(52.8%)	-2.2(0.2%)	166.1	0.36

[M(Gly1)]²⁺	ΔE _inter	ΔE _orb	ΔE _ex	ΔE _els	ΔE _disp	ΔE _deform	ΔQ
[Sc(Gly1)]²⁺	-753.3	-439.4(52.1%)	89.4	-402.6(47.8%)	-0.7(0.1%)	158.1	0.23
[Ti(Gly1)]²⁺	-845.1	-471.1(51.0%)	78.5	-451.7(48.9%)	-0.7(0.1%)	188.3	0.31
[V(Gly1)]²⁺	-893.4	-542.2(54.2%)	107.0	-457.5(45.7%)	-0.8(0.1%)	221.3	0.38
[Cr(Gly1)]²⁺	-960.4	-583.5(55.5%)	90.8	-467.2(44.4%)	-0.6(0.1%)	197.2	0.42
[Mn(Gly1)]²⁺	-858.5	-414.4(43.8%)	87.8	-531.1(56.1%)	-0.8(0.1%)	183.7	0.27
[Fe(Gly1)]²⁺	-901.0	-490.3(49.1%)	97.1	-506.8(50.8%)	-1.0(0.1%)	163.1	0.35
[Co(Gly1)]²⁺	-1024.7	-572.5(51.4%)	88.5	-540.0(48.5%)	-0.8(0.1%)	199.1	0.44
[Ni(Gly1)]²⁺	-1076.8	-611.9(52.1%)	98.5	-562.5(47.8%)	-0.8(0.1%)	227.5	0.53
[Cu(Gly1)]²⁺	-1184.6	-679.2(52.7%)	103.3	-608.0(47.2%)	-0.8(0.1%)	214.5	0.65
[Zn(Gly1)]²⁺	-998.4	-482.1(43.1%)	119.7	-635.3(56.8%)	-0.8(0.1%)	179.9	0.37

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密度泛函理论方法研究第一系列过渡金属对甘氨酸的配位能力

Density functional theory study on coordination ability of glycineand the first series transition metals

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