Salen型铜(Ⅱ)和镍(Ⅱ)配合物的合成与电化学性质

doi:10.3724/SP.J.1095.2014.30166

摘要/Abstract

摘要： 合成了2种salen型配体及其具有N2O2配位模式的salen型铜、镍金属配合物ML1和ML2[M=Cu,Ni;salen型配体L1=N,N′-双(4-羟基-邻羟苯亚甲基)-2,2′-联苯二胺;L2=N,N-′双(3,5-二叔丁基-邻羟苯亚甲基)-2,2′-联苯二胺]；并通过核磁共振波谱（1H NMR）、电喷雾质谱（ESI-MS）、红外光谱（FT-IR）、紫外-可见光谱（UV-Vis）和元素分析等对配体及目标金属配合物进行了表征。循环伏安法电化学研究发现，在-1.5～+1.5 V电势扫描中，CuL2和NiL1只有一组单电子准可逆氧化还原过程,而NiL2发生了两次氧化还原反应。

关键词: salen型配体, 铜(Ⅱ)和镍(Ⅱ)配合物, 合成和表征, 循环伏安法, 电化学性质

Abstract: Two salen-type ligands and their metal complexes(ML1 and ML2, M=Cu or Ni, L1=N,N′-bis(4-hydroxysalicylidene)-2,2′-biphenyldiamine, L2=N,N′-bis(3,5-di-tert-butyl-salicylidene)-2,2′-biphenyldiamine) with tetradentate N2O2 coordinate mode were synthesized. These complexes were characterized with 1H nuclear magnetic resonance(1H NMR), ultraviolet-visible absorption spectroscopy(UV-Vis), Fourier transform infrared spectroscopy(FT-IR), mass spectrometry(MS), and elemental analyses. The electrochemical properties of the synthesized complexes were also studied by cyclic voltammetry(CV). The CV curves of CuL2 and NiL1 only contained a one-electron quasi-reversible redox peak in the range of -1.5~+1.5 V. In contrast, two redox peaks were observed in the CV curve of NiL2.

Key words: salen-type ligand, copper(Ⅱ) and nickel(Ⅱ) complexes, synthesis and characterization, cyclic voltammetry, electrochemical property

中图分类号:

O641

王建辉, 郭莉芹, 阮文娟, 朱志昂. Salen型铜(Ⅱ)和镍(Ⅱ)配合物的合成与电化学性质[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30166.

WANG Jianhui, GUO Liqin, RUAN Wenjuan*, ZHU Zhiang. Synthesis and Electrochemical Properties of Salen-type Copper(Ⅱ) and Nickel(Ⅱ) Complexes[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30166.

参考文献

[1] Naskar S,Naskar S,Mayer-Figge H,et al. Synthesis, X-ray Crystal Structures, Spectroscopic and Cyclic Voltammetric Studies of Cu(Ⅱ) Schiff Base Complexes of Pyridoxal[J]. Polyhedron,2011,30(3):529-534.

[2] Mariappan M,Suenaga M,Mukhopadhyay A,et al. Synthesis, Structure, DNA Binding and Photonuclease Activity of a Nickel(Ⅱ) Complex with a N,N′-Bis(salicylidene)-9-(3,4-diaminophenyl)acridine Ligand[J]. Inorg Chim Acta,2012,390:95-104.

[3] Bahaffi S O,Aziz A A A,El-Naggar M M. Synthesis, Spectral Characterization, DNA Binding Ability and Antibacterial Screening of Copper(Ⅱ) Complexes of Symmetrical NOON Tetradentate Schiff Bases Bearing Different Bridges[J]. J Mol Struct,2012,1020:188-196.

[4] Wang F,Zhang H,Li L,et al. Synthesis and Characterization of Chiral Nickel(Ⅱ) Schiff Base Complexes and Their CD Spectra-absolute Configuration Correlations[J]. Tetrahedron:Asymmetry,2006,17:2059.

[5] Wu S Z,Lu S W. Novel Nickel(Ⅱ) and Cobalt(Ⅱ) Catalysts Based on Poly-salen Type Ligands for the Dimerization of Propylene[J]. J Mol Catal A:Chem,2003,197:51-59.

[6] Paschke R,Balkow D,Sinn E. Lowering Melting Points in Asymmetrically Substituted Salen-Copper(Ⅱ) Complexes Exhibiting Mesomorphic Behavior.Structure of the Mesogen Cu(5-hexyloxySalen)[J]. Inorg Chem,2002,41(7):1949-1953.

[7] Magnus K A,Ton-That H,Carpenter J E. Recent Structural Work on the Oxygen Transport Protein Hemocyanin[J]. Chem Rev,1994,94(3):727-735.

[8] Ueno T,Ohashi M,Kono M,et al. Crystal Structures of Artificial Metalloproteins:Tight Binding of FeⅢ(Schiff-Base) by Mutation of Ala71 to Gly in Apo-Myoglobin[J]. Inorg Chem,2004,43(9):2852-2858.

[9] Carey J R,Ma S K,Pfister T D,et al. A Site-Selective Dual Anchoring Strategy for Artificial Metalloprotein Design[J]. J Am Chem Soc,2004,126(35):10812-10813.

[10] Solomon E I,Chen P,Metz M,et al. Oxygen Binding, Activation, and Reduction to Water by Copper Proteins[J]. Angew Chem Int Ed,2001,40:4570-4590.

[11] Chen J M,Ruan W J,Meng L,et al. Spectroscopic and Theoretical Studies on Axial Coordination of Bis(pyrrol-2-ylmethyleneamine)phenyl Complexes[J]. Spectrochim Acta Part A,2008,71(1):191-198.

[12] Xie M,Li L,Yang X,et al. A New Insulin-enhancing Agent:[N,N′-Bis(4-hydroxysalicylidene)-o-phenylene-diamine]oxovanadium(Ⅳ) and Its Permeability and Cytotoxicity[J]. Eur J Med Chem,2010,45(6):2327-2335.

[13] GUO Liqin,SHI Xiuli,RUAN Wenjuan,et al. Synthesis and Characterization of Novel Salen-Type Complexes and Their Axial Coordination Thermodynamics[J]. Acta Phys-Chim Sin,2010,26(5):1195-1201(in Chinese).

]郭莉芹,史秀丽,阮文娟,等. 新型Salen型配合物的合成和表征及轴向配位热力学[J]. 物理化学学报,2010,26(5):1195-1201.

[14] ZHAO Xiaojing,RUAN Wenjuan,ZHU Zhi′ang,et al. Study on Synthesis and Spectral Properties of Porphyrin-salen Compounds[J]. Chinese J Org Chem,2006,26(8):1087-1092(in Chinese).

]赵小菁,阮文娟,朱志昂,等. 卟啉-salen化合物的合成及谱学性质研究[J]. 有机化学,2006,26(8):1087-1092.

[15] Hatcher L,Karlin K D. Oxidant Types in Copper-dioxygen Chemistry:the Ligand Coordination Defines the Cun-O2 Structure and Subsequent Reactivity[J]. J Biol Inorg Chem,2004,9:669-683.

[16] 2]Synthesis and Crystal Structure of a Copper(Ⅱ) Complex of Deprotonated N,N′-Bis(2-pyridinecarboxamide)-2,2′-biphenyl:]Comparative Redox Study of CuN4 Pyridine Amide Complexes[J]. Inorg Chim Acta,2007,360(10):3456-3461.

[17] D Perrin D,Armarego W L,Perrin D R. Purification of Laboratory Chemicals[M]. 2nd Ed. Pergamon:Oxford,1982.

[18] Kornblum N,Kendall D L. The Use of Dimethylformamide in the Ullmann Reaction[J]. J Am Chem Soc,1952,74(22):5782.

[19] Larrow J F,Jacobsen E N,Gao Y,et al. A Practical Method for the Large-Scale Preparation of [N,N′-Bis(3,5-di-tertbutylsalicylidene)-1,2-cyclohexanediaminato(2-)]manganese(Ⅲ) Chloride, a Highly Enantioselective Epoxidation Catalyst[J]. J Org Chem,1994,59(7):1939-1942.

[20] Boghaei D M,Behzad M. Synthetic Study of Symmetrical and Unsymmetrical Schiff Base Complexes of VO(Ⅳ) and Mn(Ⅲ) Derived from 2,2′-Diaminobiphenyl[J]. Synth React Inorg Met-Org Chem,2005,35(4):261-267.

[21] Rabie U M,Assran A S A,Abou-El-Wafa M H M. Unsymmetrical Schiff Bases Functionalize as Bibasic Tetradentate(ONNO) and Monobasic Tridentate(NNO) Ligands on Complexation with Some Transition Metal Ions[J]. J Mol Struct,2008,872:113-122.

[22] Khandar A A,Shaabani B,Belaj F,et al. Synthesis, Characterization and Spectroscopic and Electrochemical Studies of New Axially Coordinated Cobalt(Ⅲ) Salen(salen=N,N′-Bis(salicylidene)-1,2-ethylenediamine) Complexes. The crystal structure of [CoⅢ(salen)(aniline)2]ClO4[J]. Polyhedron,2006,25(9):1893-1900.

[23] Zhang J,Zhang W,Luo Q,et al. Non-template Synthesis and Electrospray Mass Spectrometric Study of Some Lanthanide(Ⅲ) Complexes[J]. Polyhedron,1999,18(27):3637-3642.

[24] Clarke L P,Davies J E,Raithby P R,et al. Synthesis, Characterisation and Electrochemistry of the Novel Ferrocenyl-dienediyltriosmium Cluster [Os3(CO)9{μ3-η4-Fe[C5H4(C2SiMe3)]2}[J]. J Chem Soc Dalton Trans,1996,(22):4147-4148.

[25] 2]Zolezzi S,Spodine E,Decinti A. Electrochemical Studies of Copper(Ⅱ) Complexes with Schiff-base Ligands[J]. Polyhedron],2002,21:55-59.

[26] Hormnirun P,Marshall E L,Gibson V C,et al. Study of Ligand Substituent Effects on the Rate and Stereoselectivity of Lactide Polymerization Using Aluminum Salen-type Initiators[J]. PNAS,2006,103(42):15343-15348.

[27] 2]Klement R,Stock F,Elias H,et al. Copper(Ⅱ) Complexes with Derivatives of salen and Tetrahydrosalen: a Spectroscopic,] Electrochemical and Structural Study[J]. Polyhedron,1999,18:3617-3628.

[28] HUANG Junli,BAO Zhiyu. Ultraviolet Absorption and Its Application[M]. 1st Ed. Beijing:Science and Technology Press of China,1992(in Chinese).

]黄君礼，鲍治宇编著. 紫外吸收光谱法及其应用[M]. 北京:中国科学技术出版社出版，1992.

[29] Bella S D,Fragalà I,Ledoux I,et al. Synthesis, Characterization, Optical Spectroscopic, Electronic Structure, and Second-Order Nonlinear Optical(NLO) Properties of a Novel Class of Donor-Acceptor Bis(salicylaldiminato) Nickel(Ⅱ) Schiff Base NLO Chromophores[J]. J Am Chem Soc,1997,119(40):9550-9557.

[30] Pui A,Policar C,Mahy J. Electronic and Steric Effects in Cobalt Schiff Bases Complexes: Synthesis, Characterization and Catalytic Activity of Some Cobalt(Ⅱ) Tetra-halogens-dimethyl Salen Complexes[J]. Inorg Chim Acta,2007,360(6):2139-2144.

[31] LIU Jia,GUO Liqin,ZHANG Xiaohong,et al. Synthesis, Characterization and Properties of Salen-Type Complexes[J]. Acta Phys Chim Sin,2012,28(2):265-272(in Chinese).

]刘佳,郭莉芹,张晓红,等. Salen型化合物的合成、表征及性质[J]. 物理化学学报,2012,28(2）:265-272.

[32] Fabbrizzi L,Poggi A,Zanello P. Oxidation and Reduction of Copper(Ⅱ) Complexes with Saturated Polyaza Macrocycles of Varying Size and Denticity[J]. J Chem Soc Dalton Trans,1983:2191-2195.

[33] Zanello P,Seeber R,Cinquantini A,et al. Electrochemical Behaviour of Complexes of Copper(Ⅱ) with 14-Membered Saturated Tetra-aza Macrocycles[J]. J Chem Soc Dalton Trans,1982:893.

[34] Sarkar B,Bocelli G,Cantoni A,et al. Copper(Ⅱ) Complexes of Symmetrical and Unsymmetrical Tetradentate Schiff Base Ligands Incorporating 1-Benzoylacetone: Synthesis, Crystal Structures and Electrochemical Behavior[J]. Polyhedron,2008,27:693-700.

[35] Elder R C,Hill M C. A Distorted Tetrahedral Copper(Ⅱ) Complex of a Tetradentate Schiff Base Ligand[J]. Inorg Chem,1979,18(3):729-732.

[36] Fernandez-G J M,Acevedo-Arauz E,Cetina-Rosado R. Electrochemical Studies of Copper(Ⅱ) Complexes Derived from Bulky Schiff Bases:the Crystal Structure of Bis[N-(1-adamantyl)-salicylaldiminato]Copper(Ⅱ)[J]. Transition Met Chem,1999,24:18-24.

[37] Zanello P,Cinquantini A. Electrochemical Behaviour of a Series of N,N′-1,2-Phenylenebis(salicylideneimin)ato Transition Metal Complexes[J]. Transition Met Chem,1985,10:370-374.

[38] Zanello P,Tamburini S,Vigato P A,et al. Electrochemistry of Transition Metal Complexes of Schiff Base Compartmental Ligands[J]. Transition Met Chem,1984,9(5):176-180.