كمپلكس هاي تك هسته اي مس ﴿II﴾ با ليگاندهاي پلي پيريديلي 2، 4، 6- تريس ﴿ 2- پيريديل﴾ - 1، 3، 5- تري آزين ﴿tpta ﴾ و بيس ﴿2- پيريديل كربونيل﴾ آميدو ﴿bpca ﴾؛ بررسي اثر كاتاليزوري مس ﴿II﴾ در هيدروليز ليگاند tptz

چكيده انگليسي :

Mononuclear Cu II complexes with polypyridyl ligands 2 4 6 tris 2 pyridyl 1 3 5 triazine tptz and bis 2 pyridylcarbonyl amido bpca Study of catalytic effect of Cu II in hydrolysis reaction of tptz Khatereh Abdi k abdi@ch iut ac ir Date of Submission 2009 10 31 Department of Chemistry Isfahan University of Technology Isfahan 84156 83111 Iran Degree M Sc Language FarsiSupervisor Hassan Hadadzadeh hadad@cc iut ac irAbstract In this thesis two mononuclear polypyridyl complexes of Cu II Cu tptz Cl2 2H2O and Cu tptz 2 PF6 2 CH3CN where tptz is 2 4 6 tris 2 pyridyl 1 3 5 triazine have been prepared andcharacterized by elemental analysis FT IR and UV Vis spectroscopies Solid state structures of bothcomplexes were determined by single crystal X ray crystallography Green crystals of Cu tptz Cl2 weregrown by ether diffusion into a methanol solution of the complex In this complex Cu II is five coordinateand the tptz ligand is coordinated as a tridentate chelate with one Ntriazine and two Npyridyl atoms The FT IRspectrum of this complex shows that C N and C C bonds shift to higher frequencies in comparison to freetptz ligand Electronic spectrum of this complex was taken in methanol The intense absorption bands seenin the UV region are assigned to ligand centered transitions and a weak absorption band seen in the visibleregion is assigned to d d transition Elemental analysis and ORTEP drawing of this complex shows that Cu tptz Cl2 is crystallized with two water molecules Air stable Green crystals of Cu tptz 2 PF6 2 were grown by slow evaporation of an acetonitrile toluenesolution of the complex In this complex the tptz ligands are tridentate and linked to the Cu II via three Natoms and the CuN6 entities have compressed octahedral geometry with the shortest Cu N bonds that formthe axial positions It represents Z in distortion at 90 K The shortness of the Cu Ntriazine bonds comparedwith the Cu Npyridyl bonds is suggested to be due to the stronger accepting properties of the triazine ring ORTEP drawing and elemental analysis of this complex showed that Cu tptz 2 PF6 2 crystallized with anacetonitrile molecule The lattice structure is further stabilized by a network of weak hydrogen bondsbetween the H atoms of the pyridyl rings of the tptz ligand and the F atoms of PF6 anions The FT IRspectrum of the complex shows a sharp and intense absorption band around 840 cm 1 for the P F Theintense absorption bands seen in the UV region of Electronic spectrum of this complex are assigned toligand centered transitions and a weak absorption band seen in visible region is a d d transition Catalytic effect of Cu II in hydrolysis reaction of tptz was studied Hydrolysis of aqueous solution of Cu tptz Cl2 2H2O produces the coordination polymer Cu bpca Cl n where bpca isbis 2 pyridylcarbonyl amido ligand The Cu bpca Cl n complex was characterized by elemental analysis FT IR and UV Vis spectroscopies and X ray crystallography The structural determination shows that the Cu bpca Cl n complex is a 1D coordination polymer and the Cu II ions are five coordinate with distortedsquare pyramidal geometry A careful inspection of the packing pattern in the lattice of the complex revealsthat noncovalent interaction of C H O type are active in the lattice The FT IR spectrum of Cu bpca Cl ncomplex exhibits a sharp band at 1716 cm 1 that is ascribable to a stretching frequency of the C O bands onthe bpca ligand The qualitative observation of hydrolysis reaction by UV Vis spectroscopy in LF region showed anisosbestic point The presence of this isosbestic point shows that the concentration of intermediate s isconstant Keywords Cu II complexes Polypyridyl ligands 2 4 6 Tris 2 pyridyl 1 3 5 triazine Bis 2 pyridylcarbonyl amido Crystal structure Z in distortion Isosbestic point

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