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Synthesis and Characterization of Chiral Heteronuclear Complexes of Schiff Base Containing Dipeptide

Author: ZhangYanYan
Tutor: LiuWenLong；HuXiaoYa
School: Yangzhou University
Course: Analytical Chemistry
Keywords: Dipeptide Heteronuclear complexes of chiral Complex Ligand Schiff base
CLC: O641.4
Type: Master's thesis
Year: 2008
Downloads: 85
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Abstract


Chiral-polynuclear metal complexes have broad application prospects, it has become in recent years a hot research field. In addition to a variety of structure types and bonding way, it has many special performance. Plays an important role in the life processes of metalloproteins and metalloenzymes proceed heterotrophic dual-core structure, the chiral Heteromultimetallic complexes are widely used as a metal protein active site model in the study of biological inorganic chemistry very important class of complexes. Therefore, in-depth understanding of the the heteronuclear complexes law chiral structural regularity and performance in recent years, chemists, biochemists and materials scientists pursue goals. This thesis three different R group side chain of the amino acid composition of the dipeptide as a chiral molecule with salicylaldehyde and its derivatives condensation synthesis of chiral Schiff base ligand, with copper complex to form a rigid \and assembled molecular base block with alkali metals, alkaline earth metals and transition metal coordination further, designed to build a series of Heterobinuclear Heteromultimetallic, one-dimensional, two-dimensional structure Heteromultimetallic carboxyl Bridged Complexes. These polynuclear complexes with optically active. Salicylaldehyde and Gan Liang dipeptide condensation with copper ligand chiral complexes ligand [CuL] -, and further coordination of the transition metal ions and alkali metal, have different nuclear chiral complexes of Cu (Ⅱ)-M (Ⅱ) (M = Ba, Sr, Cd, Mg, Ni), and characterized by elemental analysis, IR, UV, TG, conducted the study of the nature of X-ray single crystal diffraction and circular dichroism spectra of the five complexes and structural characterization. Wherein the complex (1) - (2) The crystal structure is very similar to the bridging effect of the carboxyl group formed by an M-Cu-M Heterotrinuclear complexes. Molecules via intermolecular hydrogen bonding, and molecular hydrogen bonding interactions within the complex three-dimensional spatial network structure constitutes a chiral. Similar to the crystal structure of the complex (3) - (5) are formed, in their crystal structure stacking disaggregated [M (H 2 O) 6 ] < sup> 2 cation column and [CuL] - anion column arrangement, cation column and anionic column connected by hydrogen bonds to form a three-dimensional network structure of the chiral space. Their CD spectra show a negative Cotton effect is described having an optically active. Gan salicylaldehyde and chiral Valerian dipeptide condensation of Schiff base copper formed complexes molecule-based block further coordination with metal ions design built into the Cu (II)-M (II) ( M = Ba, Ni) chiral heteronuclear metal complexes, and by elemental analysis, IR, UV, TG, they carried out a study of the nature and structural characterization by X-ray diffraction and circular dichroism spectra. Complexes (6) The crystal structure of the octahedron p21 chiral space group, each unit cell contains a [Ba (H 2 O) 5 ( CuL) 2 ] trinuclear unit and a free water. Molecule by a bridging effect of the carboxyl group to form a structure of a Ba-Cu-Ba Heterotrinuclear. Molecules along the a-axis direction is formed the coupled secondary helical chains by hydrogen bonds, forming another hydrogen coupling secondary helical chains along the b-axis direction, the two chains interleaved coupled to each other through hydrogen bonding, the formation of hydrogen-coupled honeycomb shaped chiral structure. The crystal structure of the complex (7) formed along the c-axis direction, the disaggregated Ni (H 2 O) 5 (CH 3 OH)] 2 cation column and [CuL] - anion column arrangement, the cation column and anion column through the hydrogen bonds link the formation of a three-dimensional network structure of chiral. CD spectra of the complexes (6) 7 diagram shows the transition from a negative Cotton effect by copper dd, having an optical activity. Series of chiral heteronuclear complexes - methoxysalicylaldehyde galanin, Gan Valerian, Gan Liang dipeptide condensation build get to form Schiff alkali and alkaline earth metal ions. Complex (8) of the structure and the structure of the complex (9) are similar, each unit cell contains a single nuclear [CuL 1 ] - unit, and a dual-core M (H 2 O) 5 [CuL 1 ] unit, [CuL 1 ] - oxygen as a tridentate ligand with a methyl group, two carboxyl oxygen chelated metal ion M, the molecules along the a-axis direction to form the anion and cation of the one-dimensional interleaving chain, stacked along the b-axis direction secondary helical chain, hydrogen bonding is formed between the chain and the chain connected via hydrogen bonds to form a three dimensional chiral structure. Complex (10) of the dipeptide by Gan malonate peptide replaced Gan Valerian a dipeptide, the side chain substituted on the methyl group from the dipeptide into an isopropyl group, but the structure (8), (9) is similar. Complex (11) in the dipeptide change into a sweet light dipeptides and dipeptide side chain substituent groups into isobutyl structure also changed. Each unit cell contains two [CuL 3 ] - unit, a Mg (H 2 O) 6 2 unit, and three free water. Disaggregated formed in the crystal structure of the heap [Mg (H 2 O) 6 ] 2 cation column and CuL3] - The anion column arranged, the cation column and anion column connected by hydrogen bonds to form a three-dimensional chiral space mesh structure. 4 obtained DL-Gan malonate peptide and 5 - sulfosalicylamide aldehyde condensation and copper ligand complex ligands [CuL] 2 -, and further reacted with an alkaline earth metal ion Ca 2 Sr 2 Ba 2 reaction, get the three carboxy and sulfo bridging heteronuclear coordination polymer {[Ca (H 2 O) 5 (CuL)] · 5H 2 O} n (12), {[Sr (H 2 O) the the 4 (CuL)] · 5 H 2 O} n (13) and {[Ba (H 2 < / sub> O) 5 (CuL)] · 5H 2 O} n (14). Complexes {[Ca (H 2 O) 5 (CuL)] · 5H 2 O} n ( 12) the Ca 2 of the relatively small atomic radius, so only a sulfo oxygen involved in the coordination, then a one-dimensional chain coordination polymer formed by carboxyl bridging effect; fit object {[Sr (H 2 O) 4 (CuL)] · 5H 2 O} n (13 ) and {[Ba (H 2 O) 5 (CuL)] · 5H 2 O} n ( 14) structurally similar, have two sulfo oxygen involved in the coordination, the formation of a two-dimensional grid-like structure of the ligand polymer; the three complexes carboxyl oxygen are in the form of μ2 ligand.

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Structural Chemistry > Complex chemistry ( coordination chemistry )
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