سنتز، شناسايي و تعيين ساختار كمپلكس هاي ارتوپالاديت با ليگاند2- فنيل آنيلين، كاربرد آنها در واكنش سوزوكي، هك و تهيه كاتاليست ناهمگن بر بستري از تيتانيم اكسيد

چكيده انگليسي :

Synthesis and Characterization of Orthopalladated Complexes with 2 Phenylaniline Their Catalytic Application in The Suzuki Heck Reactions and Preparation of Heterogeneous Catalyst with TiO2 Naser Rahimi nrahimi iut@yahoo com Date of Submission 2011 3 12 Department of Chemistry Isfahan University of Technology Isfahan 84156 83111 Iran Degree M Sc Language FarsiSupervisor Kazem Karami Karmi@cc iut ac irAbstractIn this thesis dinuclear complex Pd 2 N2 C1 2 2 NH2C6H4 C6H4 Cl 2 was synthesized by treating thesystem 2 phenylaniline PdCl2 NaCl NaOAc in a molar ratio of 1 1 2 1 in methanol at room temperature for oneweek This complex precipitated in the reaction medium was isolated by filtration and purified by washingadequate solvents In the IR of Pd 2 N2 C1 2 2 NH2C6H4 C6H4 Cl 2 the asymmetric and symmetricstretchings of the amino group appeared in lower frequency in comparison to free 2 phenylaniline ligand Thereaction of dinuclear complex and monodentate ligands L pyridine 4 picoline symcollidine gavemononuclear orthopalladated complexes Pd 2 N2 C1 2 2 NH2C6H4 C6H4 py Cl Pd 2 N2 C1 2 2 NH2C6H4 C6H4 4 Mepy Cl and Pd 2 N2 C1 2 2 NH2C6H4 C6H4 sym collidine Cl in the condition ofTHF acetone 15 5 as solvent room temperature and 6h The dinuclear complex was reacted with AgX X CF3SO3 BF4 to remove the Cl bridges in 30 minutes then addition of bidentate ligands such as phen bipyridine bipy 1 2 bis diphenyl phosphino ethane dppe 1 3 bis diphenylphosphino propane dppp topreparation of mononuclear orthopalladated complexes Pd 2 N2 C1 2 2 NH2C6H4 C6H4 phen Pd 2 N2 C1 2 2 NH2C6H4 C6H4 bipy Pd 2 N2 C1 2 2 NH2C6H4 C6H4 dppe and Pd 2 N2 C1 2 2 NH2C6H4 C6H4 dppp The complexes were chracterized by FT IR 1H NMR 13C NMR 31P NMR and X raydiffraction study of Pd 2 N2 C1 2 2 NH2C6H4 C6H4 sym collidine Cl In the FT IR of all compounds the difference in N H and in some of them in N C bonds in comparison to free ligand is observed 1H NMR and13 C NMR showed 2 proton and carbon of the all compounds resonate at low frequencies It may be occurredbecause of anisotropic effect of aromatic ring of mono and bidentate ligands that coordinated with metalliccenter and also a reason for synthesizing mentioned compounds Moreover it shows that the monodentateligands and palladated phenyl ring are in cis arrangement In two cases complexes Pd 2 N2 C1 2 2 NH2C6H4 C6H4 dppe and Pd 2 N2 C1 2 2 NH2C6H4 C6H4 dppp the 31P NMR was recorded thatchemical shift of the phosphorus nucleus was in the reasonable interval from free ligands In the 31P NMR offree dppe and dppp only one peak is observed but in these complexes two and four peaks wewr recorded for Pd 2 N2 C1 2 2 NH2C6H4 C6H4 dppe and Pd 2 N2 C1 2 2 NH2C6H4 C6H4 dppp respectively Informer two peaks is because of difference in trans group and for the latter two excess peaks may be due toopening the formed chelate by dppp ligand that is caused the free phosphorus atom sense different electronicspace s Moreover The X ray crystal structure of compound Pd 2 N2 C1 2 2 NH2C6H4 C6H4 sym collidine Cl was determined This complex crystallized in the monoclinic space group P21 n Thus two pairsof enantiomeric molecules were present in the unit cell of it Z 4 and also proved that monodentate ligandsare in the trans arrangement with amino group After characterization the complexes were tested in the Suzukiand the Heck reactions that the catalytic activity was much more better in former one In the coupling reactions various aryl bromides in functional group phenylboronic acid for the Suzuki reaction and styrene for the Heckreaction were used The effectiveness of different group such as CHO OMe was evaluated Finally Pd 2 N2 C1 2 2 NH2C6H4 C6H4 phen with TiO2 reacted in water to prepare ancompoundheterogeneous catalyast in safe and facile method that SEM analyzing showed it is synthesized in nano scale Key words 2 Phenylaniline Orthopalladated complexes Suzuki reaction Heck raction

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سنتز، شناسايي و تعيين ساختار كمپلكس هاي ارتوپالاديت با ليگاند2- فنيل آنيلين، كاربرد آنها در واكنش سوزوكي، هك و تهيه كاتاليست ناهمگن بر بستري از تيتانيم اكسيد

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