含咪唑盐的三联吡啶铜配合物的合成和分子结构

doi:10.11944/j.issn.1000-0518.2016.02.150194

摘要/Abstract

摘要：

通过带有不同长度的4-(4-氯烷氧基苯基)-2,2':6,2″-三联吡啶和N-甲基咪唑在甲苯中加热反应,制备了3种由烷氧基桥联的新型三联吡啶咪唑配体。研究了配体和过渡金属离子的配位反应。测定了三联吡啶咪唑铜配合物的单晶分子结构,在铜配合物中,Cu(Ⅱ)和两个三联吡啶单元形成扭曲八面体配位方式。Monoclinic,空间群P 21/c;a=1.7229(3) nm,b=1.5924(2) nm,c=2.1590(3) nm,α=90°,β=101.332(2)°,γ=90°,M_r=1298.09,V=5.8078(15) nm³,D_c=1.485 mg/m³,Z=4, F(000)=2684。

关键词: 三联吡啶, 咪唑盐, 金属配合物, 晶体结构

Abstract:

A series of functionalized terpyridine ligands containing alkyl bridged imidazolium salts were designed and prepared in convenient manner. The transition metal complexes of these functionalized terpyridine ligands were investigated and the single crystal structure of Cu complex was successfully determined by X-ray diffraction. In the copper complex, Cu²⁺ was coordinated with two terpyridine units to form distorted octahedron symmetry. Monoclinic, space group P 21/c; a=1.7229(3) nm, b=1.5924(2) nm, c=2.1590(3) nm, α=90°, β=101.332(2)°, γ=90°, M_r=1298.09, V=5.8078(15) nm³, D_c=1.485 mg/m³, Z=4, F(000)=2684.

Key words: terpyridine, imidazolium salt, transition metal complex, crystal structure

穆华荣, 毕欣, 孙晶, 颜朝国. 含咪唑盐的三联吡啶铜配合物的合成和分子结构[J]. 应用化学, 2016, 33(2): 206-212.

MU Huarong, BI Xin, SUN Jing, YAN Chaoguo. Synthesis and Molecular Structure of Copper Complex of Terpyridine Bearing with Imidazolium Salts[J]. Chinese Journal of Applied Chemistry, 2016, 33(2): 206-212.

参考文献

[1]	Sauvage J P,Collin J P,Chambron J C,et al.Ruthenium(Ⅱ) and Osmium(Ⅱ) Bis(terpyridine) Complexes in Covalently-Linked Multicomponent Systems:Synthesis, Electrochemical Behavior, Absorption Spectra, and Photochemical and Photophysical Properties[J]. Chem Rev,1994,94(4):993-1019.
[2]	Barigelletti F,Flamigni L. Photoactive Molecular Wires Based on Metal Complexes[J]. Chem Soc Rev,2000,29(1):1-12.
[3]	Hofmeier H,Schubert U S. Recent Developments in the Supramolecular Chemistry of Terpyridine-metal Complexes[J]. Chem Soc Rev,2004,33(6):373-399.
[4]	Constable E C. 2,2':6',2″-Terpyridines: From Chemical Obscurity to Common Supramolecular Motifs[J]. Chem Soc Rev,2007,36(2):246-253.
[5]	Bazzicalupi C,Bencini A,Bianchi A,et al.Coordination Properties of Polyamine-macrocycles Containing Terpyridine Units[J]. Coord Chem Rev,2008,252(10/11):1052-1068.
[6]	Cummings S D. Platinum Complexes of Terpyridine: Interaction and Reactivity with Biomolecules[J]. Coord Chem Rev,2009,253(9/10):1495-1516.
[7]	Sun J,Xia E Y,Yan C G. Syntheses and Structures of Mn(Ⅱ), Co(Ⅱ), and Zn(Ⅱ) Complexes of 1,3-Diterpyridyl-substituted p-tert-Butylcalix[4]arene[J]. J Cood Chem,2012,65(17):3086-3097.
[8]	YAN Xiaohua,DU Liting,BI Xin,et al.Efficient Synthesis of Alkoxyl Bridging Bisterpyridines[J]. Chinese J Org Chem,2010,30(12):1955-1959(in Chinese). 严晓华,杜丽婷,毕欣,等. 烷氧基桥联三联吡啶的合成[J]. 有机化学,2010,30(12):1955-1959.
[9]	Li L,Du L T,Sun J. Synthesis, Crystal Structure of Bis-terpyridinyl-calix[4]arene Derivatives and Fluorescent Sensor for Zinc Ion[J]. Chem Res Chinese Univ,2013,29(5):874-878.
[10]	Herrmann W A. N-Heterocyclic Carbenes:A New Concept in Organometallic Catalysis[J]. Angew Chem Int Ed,2002,41(8):1290-1309.
[11]	Budagumpi S,Kim K H,Kim I. Catalytic and Coordination Facets of Single-site Non-metallocene Organometallic Catalysts with N-Heterocyclic Scaffolds Employed in Olefin Polymerization[J]. Coord Chem Rev,2011,255(23/24):2785-2809.
[12]	Budagumpi S,Haque R A,Salman A W. Stereochemical and Structural Characteristics of Single- and Double-site Pd(Ⅱ)-N-heterocyclic Carbene Complexes:Promising Catalysts in Organic Syntheses Ranging from C-C Coupling to Olefin Polymerizations[J]. Coord Chem Rev,2012,256(17/18):1787-1830.
[13]	Crabtree R H. Abnormal,Mesoionic and Remote N-Heterocyclic Carbene Complexes[J]. Coord Chem Rev,2013,257(3/4):755-766.
[14]	Lin J C Y,Huang R T W,Lee C S,et al. Coinage Metal—N-Heterocyclic Carbene Complexes[J]. Chem Rev,2009,109(8):3561-3598.
[15]	Marion N,Nolan S P. Well-Defined N-Heterocyclic Carbenes-Palladium(Ⅱ) Precatalysts for Cross-Coupling Reactions[J]. Acc Chem Res,2008,41(18):1440-1449.
[16]	Poyatos M,Mata J A,Peris E. Complexes with Poly(N-heterocyclic carbene) Ligands:Structural Features and Catalytic Applications[J]. Chem Rev,2009,109(8):3677-3707.
[17]	Budagumpi S,Endud S. Group XII Metal-N-Heterocyclic Carbene Complexes:Synthesis, Structural Diversity, Intramolecular Interactions, and Applications[J]. Organometallics,2013,32(6):1537-1562.
[18]	Gu W W,Chen W J,Yan C G. Synthesis and Crystal Structures of Ag and Hg Complexes of Bis(N-heterocyclic carbenes) on p-tert-Butylcalix[4]arene Plateform[J]. Supramol Chem,2015,27(2):407-413.
[19]	Manikandamathavan V M,Nair B U. DNA Binding and Cytotoxicity of Copper(Ⅱ) Imidazole Terpyridine Complexes: Role of Oxyanion, Hydrogen Bonding and π-π Interaction[J]. Eur J Med Chem,2013,68:244-252.
[20]	Huang W,You W,Wang L, et al, Anionic Effects on the Formation of Tridentate 4'-Chloro-2,2':6',2"-terpyridine Copper(Ⅱ) Complexes Having 1:1 or 1:2 Ratio of Metal and Ligand and Their Crystal Symmetry[J]. Inorg Chim Acta,2009,362:2127-2135.
[21]	Martinez-Vargas S,Martinez A I,Valdés-Martínez J,et al.Preparation of Three New 4'-Phenylterpyridine-copper(Ⅱ) Complexes Containing Nicotinate or Iso-nicotinate Ligands[J]. J Mol Struct,2013,1033:34-39.