5331

5001

كارشناسي ارشد

شيمي معدني

اصفهان: دانشگاه صنعتي اصفهان، دانشكده شيمي

1388

يازده،245ص.:مصور،جدول،نمودار

ص.ع.به فارسي و انگليسي

حسن حدادزاده

علي اكبر دهنو خلجي

22/4/89

عليرضا گرجي،حسين چيني فروشان

شيمي

ID5001

به فارسي و انگليسي: قابل رويت در نسخه ديجيتالي

Mononuclear Nickel II Complexes Coordinated by 2 4 6 Tris 2 pyridyl 1 3 5 triazine tptz Theoretical and Experimental Study of the Protonatedtptz Ligand tptzH2 2 Mahboobeh Maghami m maghami@ch iut ac ir Date of Submission 2010 3 10 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 nickel II Ni tptz MeOH Cl2 and Ni tptz 2 PF6 2 CH3CN where tptz ligand 2 4 6 tris 2 Pyridyl 1 3 5 triazine have been prepared andcharacterized by elemental analysis FT IR UV Vis and 1H NMR spectroscopies Solid state structures of bothcomplexes were determined by single crystal X ray crystallography The coordination geometry around the six coordinated Ni II center in Ni tptz MeOH Cl2 complex is a distorted octahedron and tptz as a tridentate ligandoccupies three binding sites The FT IR spectrum of this complex shows the shift of C N and C C bonds tothe higher frequencies compared to free tptz ligand Based on the ORTEP diagram of Ni tptz 2 PF6 2 CH3CN complex two tridentate tptz ligands are coordinatedto the metal center through their N atoms in a mutually perpendicular fashionand and provide a distortedoctahedral geometry around Nickel The shortening of the Ni Ntriazine bonds compared to the Ni Npyridyl bonds canbe related to the stronger accepting properties of the triazine ring ORTEP drawing and elemental analysis ofthis complex confirms the presence of an acetonitrile molecule in the crystal structure The lattice structure isfurther stabilized by a network of weak hydrogen bonds between the H atoms of the pyridyl rings and the F atomsof PF6 anions The protonated form of Tptz tptzH2 PF6 2 H2O has been prepared and characterized by FT IR UV Vis 1 H NMR and fluorescence spectroscopies The solid state structure of this compound were determined by singlecrystal X ray crystallography and by computational methods using Moltran and gaussian softwares performed byDFT calculations using B3LYP 6 311 G level of theory According to the ORTEP diagram of this compound only two nitrogen atoms of the total six nitrogen atoms of tptz ligand are protonated Also there is a molecule ofwater as the crystallized solvent in the crystal structure of the compound As understood from the packingpattern the lattice structure is further stabilized by a network of non covalent interactions of the hydrogen bonds By using of B3LYP 6 311 G method FT IR spectra of tptz and tptzH and tptzH22 configurations werecalculated that showed there is a very good agreement between experimental and calculated results Furthermore 1 H NMR spectrum of tptzH22 N36N16 configuration is calculated using the B3LYP 6 311 G 2d P than TMS and comparison with experimental 1H NMR spectrum of compound tptzH2 PF6 2 H2O a very interestingdifferent case in solution and gas phase is observed The tendency to proton affinity three atoms of nitrogen of thesix nitrogen atoms once separately and then at the same time has been calculated is highly agreement betweenexperimental and calculated data Keywords Ni II complexes PolyPyridyl ligands 2 4 6 tris 2 Pyridyl 1 3 5 triazine Crystal structure Moltran Gaussian Proton affinity

حسن حدادزاده

علي اكبر دهنو خلجي

عليرضا گرجي،حسين چيني فروشان