5692

5314

كارشناسي ارشد

شيمي معدني

اصفهان: دانشگاه صنعتي اصفهان، دانشكده شيمي

1389

سيزده،210ص.: مصور،جدول،نمودار

ص.ع.به فارسي و انگليسي

كاظم كرمي

شادپور ملك پور

21/12/89

شهرام تنگستاني نژاد، حسين چيني فروشان

شيمي

ID5314

به فارسي و انگليسي: قابل رويت در نسخه ديجيتالي

100 Synthesis and characterization of ortho palladated complexes of secondaryand tertiary amines and stabilized ketophosphorus ylide and their catalytic application in Suzuki reaction Mina Mohamadi Salah m mohamadisalah@ch iut ac ir Date of Submission 2010 8 28 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 phosphorus ylides PhBPPY and BrBPPY have been synthesized through the formation ofphosphonium salt and dehydrogenation The ortho metalated complexes Pd C6H4CH2NRR XY R R H Me Et t Bu X Cl Br Y PPh3 4 Picoline sym Collidine can be prepared by refluxing equimolecular amounts of Pd OAc 2 and C6H5CH2NRR R R H Me Et t Bu in benzene for 24 h followed by addition of NaX X Cl Br in MeOH The halogeno bridges in dimeric ortho palladated complexes containing secondary and tertiary aryl alkylamines are easily cleaved by various neutral ligands including 4 Picoline sym Collidine PPh3 to affordmononuclear metallacycles These complexes can be used as the starting material for the synthesis of cyclo palladated coplexes O coordination and C coordination Pd C6H4CH2NRR XBPPY Y X Ph Br R R H Me Et t Bu X Cl Br Y PPh3 4 Picoline sym Collidine with ylide XBPPY X PH X and AgTfO reaction inTHF The CO band which is sensitive to complexation occurs from 1507 to 1519 cm 1 in the parent phosphorusylides The IR absorption band observed for these complexes show a lowering of CO indicating coordination ofthe ylide oxygen for these complexes The 1H NMR spectrum of the O bound complexes showed only one signal forthe CH methine at near to that of the free ylides and for C bound complexes the CH methine at down field The 31PNMR spectra shows a sharp signal resonance shifted slightly up field relative to the free ylide and is again inagreement with O coordination because C coordination would result in a down field shift of about 10 ppm of theylide resonance In the 13C NMR spectrum complexes 1a 3c the resonance CH2 in five membered ring in the range48 81 56 60 ppm have been observed The IR spectra of ketophosphorus ylide complex shows a sharp very strongabsorption in the 1619 cm 1 range The observation of this positive shift value for CO the complexes indicatesthat ylide be C coordinated to Pd II The 1H NMR signals for the PCH group of stabilized ketophosphorus ylidecomplex are shifted downfiled compared to that of the free ylides as a consequence of the inductive effect of themetal center The 31P NMR signals for the PCH group of complex were shifted to up field in comparison with thosein free ylides as a consequence of the inductive effects of the metal center Finally The 13C NMR signals formethine carbon appears at down field relative to the free ylide of stabilized ketophosphorus ylide complex Theresults of conductivity show that the molar activity of orthopalladated complexes are within the range for 1 1electrolytes which demonstrate the existence of the TfO as counter ion in the solution Single crystals of PhBPPYH TfO and PdCl PhBPPY PPh3 suitable for X ray crystallography were obtained The palladium atomof complex PdCl PhBPPY PPh3 are located in distorted square planer environments Palladacycle complexes havereceived great interest due to their applications in many areas such as organic synthesis Homogeneous transitionmetal catalyzed reactions represent one of the most important and well studied reaction types in microwave assistedorganic synthesis The among the various methods known to biaryl synthesis Suzuki Miyaura reaction is a powerfulmethod for the formation of C sp2 C sp2 bonds under mild reaction conditions The palladium complexes 1a 3cand PdCl PhBPPY PPh3 have been experimented as catalyst in Suzuki reaction Keyword Ortho metalated complexes Metallacycles Phosphorus ylides Suzuki reaction

كاظم كرمي

شادپور ملك پور

شهرام تنگستاني نژاد، حسين چيني فروشان