7700

7172

كارشناسي ارشد

شيمي معدني

اصفهان: دانشگاه صنعتي اصفهان، دانشكده شيمي

1391

ده،108ص.: مصور،جدول،نمودار

ص.ع.به فارسي و انگليسي

كاظم كرمي

شادپور ملك پور

17/2/92

مهدي امير نصر، حسن حدادزاده

شيمي

ID7172

به فارسي و انگليسي: قابل رويت در نسخه ديجيتالي

Synthesis of mononuclear orthopalladated complexes of 2 phenylaniline insertion of one and two molecules of symmetrical and unsymmetrical alkynes into the Pd C bond Nasrin Jamshidiyan n jamshidiyan@ch iut ac ir Date of Submission 2012 Department of Chemistry Isfahan University of Technology Isfahan 84156 83111 Iran Degree M Sc Language Farsi Supervisor Kazem Karami Karami@cc iut ac ir Abstract In this thesis an orthopalladated dimeric complex Pd C N 2 NH2C6H4 C6H4 Cl 2 A has been synthesized by reaction of PdCl2 NaCl NaOAc and 2 phenylaniline in acetone for 1 week at room temperature The chloro bridge in the dimeric orthopalladated complex A is easily cleaved by various neutral ligands including 1 10 phenanthroline 4 methyl 1 10 phenanthroline thiourea pyridine and bipyridine to afford mononuclear complexes 1 L L 1 10 phen 2 L L 4 Me phen 2 3 L tu 4 L py 5 L L bipy These complexes were fully characterized by elemental analysis IR and NMR spectroscopies In addition the crystal structure of 5 was determined by single crystal X ray diffraction analysis In this structure the palladium atom shows a slightly distorted square planar geometry The disappearance of the protons of 2 phenylaniline in the aromatic region in 1H NMR spectrum shows bidentate 4 methyl 1 10 phenanthroline ligand coordinated to the both sides of Pd atom In the second part of the project the 1 2 and 1 4 insertion reactions have been done at room temperature with symmetrical and unsymmetrical alkynes including diphenylacethylene ethylphenylacetylene carboxylate and dimethyl acetylene dicarboxylate to afford inserted dimeric and monomeric complexes 6 Pd C N 2 NH2C6H4 C6H4 Cl PhC CPh 2 7 Pd C N 2 NH2C6H4 C6H4 PhC CPh 2Cl 8 Pd C N 2 NH2C6H4 C6H4 Cl PhC CO2CH2CH3 2 9 Pd C N 2 NH2C6H4 C6H4 PhC CO2CH2CH3 2Cl 10 Pd C N 2 NH2C6H4 C6H4 Cl CH3O2C CO2CH3 2 These complexes were characterized by FT IR NMR and elemental analysis The disappearance of strong peak of C C and appearance of C C peak in the range of 1600 1640 cm 1 frequency in IR spectra of inserted complexes shows that acetylene group in alkynes convert to C C group In the last part of the project the inserted mononuclear complexes 7 and 8 have been reacted with monodentate ligand PPh3 to give complexes 11 Pd C N 2 NH2C6H4 C6H4 PhC CO2CH2 CH3 2PPh3 Cl 12 Pd C N 2 NH2C6H4 C6H4 PhC CPh 2PPh3 Cl 31 P 1H NMR spectra of the final complexes show a single peak at 25 50 ppm correspond to the coordination of PPh3 group Keywords Orthopalladated complex Insertion reaction Symmetrical and unsymmetrical alkynes

كاظم كرمي

شادپور ملك پور

مهدي امير نصر، حسن حدادزاده