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Studies On The Syntheses And Structures Of The Complexes Of Metal Ions With N- Substituted Amino Acid

Posted on:2005-09-05Degree:MasterType:Thesis
Country:ChinaCandidate:M S ChenFull Text:PDF
GTID:2121360125465076Subject:Inorganic Chemistry
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The N-sulfonyl-α-amino acids as a kind of biologically important compounds derived from naturally occurring amino acids plays an important role in participating the activity of lives. The studies of the coordination of the metal ions with N-sulfonyl-α-amino acids are important to completing and improving the system of the metal ions with amino acids. At the same time, they play a crucial role in cognizing the biological effect of metal ions as well as the mechanical function. In the dissertation, the studies on the syntheses and structures of the complexes of metal ions with N-substituted amino acid have been reviewed in detail. The synthetical condition and method of complexes have been improved; four new complexes of N- substituted amino acids have been synthesized. All of them were studied by single crystal X-ray diffraction method and were characterized by IR and elemental analysis.The two coordination polymers [Mn(bipy)(tsgluo)]n(1) and [Mn(phen) (tsgluo)]n (2) , where bipy=2,2'-bipyridine, tsgluo= N-p-tolysulfonyl- L-glutamate dianion, were synthesized in water-ethanol mixed solvent and their crystal structure were determined by X-ray diffraction analysis. They both belong to orthorhombic system with space group P212121. The cell parameters are: a = 5.3131(6)?, b = 17.727(2)?, c = 23.382(3)?,R1 = 0.0250, wR2 = 0.0649;(2):a = 5.3078(17)?, b = 17.239(5)?, c = 24.569(8)?, R1 = 0.0331, wR2 = 0.0789. The Mn atoms are octahedrally coordinated by two N atoms of one bipy (phen ) ligand and four O atoms of three Tsgluo2-. The γ-carboxyl coordinates to Mn(II) in the mode of bidentate chelate, while the α-carboxyl coordinates in bidentate bridging mode. The bridging of the α-carboxyl oxygen atoms of ligand between every two adjacent manganese ions gives rise to an infinite chain.The complex, [Nd2(TsGlyH)6(H2O)4]n·4nH2O·0.5n(CH3OH) (3), was synthesized by hydrothermal reaction under physiological pH condition. The crystal stucture of complex (3) consists of Nd3+ cations and TsglyH+ anions in the ratio 1:3. It crystallized in triclinic with space group Pī and the cell parameters are: a=12.927(1) ? b=16.841(2) ? c=17.478(2) ?, α=83.930(8)o, β= 76.23(1)o,γ=74.52(1)°,V=3557.9(7)?3,Z= 2,Dc=1.663 mg/m3. The dimeric units of [Nd2(H2O)4 (TsGlyH)6·4H2O] are bridged by four bidentate bridging carboxylate groups between Nd(1) and Nd(2) to give a B'A'ABB"A" chain, including a tridentate bridging carboxylate group. Each Nd(Ⅲ) of the dimeric unit is linked another Nd(Ⅲ) ion by bridging bidentate carboxylate groups to form a polymeric chain. The structural determination of [{Co(4,4′-bpy)2(H2O)4}{ Co2(NTA)2(4,4′-bpy)(H2O)2}] (4) reveals that the complex crystallizes in monoclinic space group P2(1)/c with the cell parameters: a = 9.1354(9) ? ,b=9.678(1) ? ,c=27.207(4) ?,α=γ=90o,β=91.562(9)o,V=2404.6(5)?3,Z=2,Dc=1.560mg/m3.There are one coordinated cation and one anion, namely mononuclear [Co(4,4′-bpy)2(H2O)4]2+ and binuclear [Co2(NTA)2(4,4′-bpy)(H2O)2]]2-. All the cobalt ions are six-coordinate with an octahedral geometry and the compound constructs a two-dimensional network via the intermolecular hydrogen bond.
Keywords/Search Tags:N-substituted amino acids, transition metal, rare earth, crystal structure
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