7033

6575

كارشناسي ارشد

شيمي معدني

اصفهان: دانشگاه صنعتي اصفهان، دانشكده شيمي

1390

يازده، 142ص.: مصور، جدول، نمودار

ص.ع. به فارسي و انگليسي

كاظم كرمي

شادپور ملك پور

15/7/91

حسين چيني فروشان، حسن حدادزاده

1396/09/18

كتابنامه

شيمي

شيمي

ID6575

به فارسي و انگليسي: قابل رويت در نسخه ديجيتالي

Synthesis of Orthopalladated Complexes Containing Phosphorus Ylide 1 3 Dichloro Propanon Ligand at Room Temprature and Their Characterization Using IR NMR Spectroscopy and X ray Crystallography Techniques Sara Amoozad s amoozad@ch iut ac ir Date of Submission 2012 2 29 Department of Chemistry Isfahan University of Technology Isfahan 84156 83111 IranDegree M Sc Language FarsiSupervisor Kazem Karami Karami@cc iut ac irAbstract In this thesis phosphonium salts I II have been synthesized through the formation of 1 3 dichloropropanon with pph3 followed by the reaction of Pd OAc 2 and the mononuclear complex Pd CHPPh3 2COCl anddinuclear complex Pd CO CH PPh3 CH2 M Cl OAc 2 have been produced The reaction of mononuclearcomplexes and bidentate ligands L phen phenanthroline 4 mepy dppe bis diphenylphosphino ethane giving themononuclear complexes Pd X CHPPh3 2CO TfO 2 X phen 4 mepy dppe and the reaction of dinuclearpalladium complexes and bidentate ligands L phen phenanthroline 4 mephen 4 methyl phenanthroline 5 NO2phen 5 NO2phenanthroline bipy 2 2 bipyridine giving the mononuclear complexes Pd X CH2 CH PPh3 COCl TfO X phen 4 mephen 5 NO2phen bipy the complexes were characterized by 1 13FT IR H NMR C NMR Termogravimetry and X ray diffraction study of Pd phen CH2 CH PPh3 COCl TfO Pd 4 mephen CH2 CH PPh3 COCl TfO The IR spectra of phosphoniumsalts show a absorption in the 1734cm 1 The frequence CO bond which is sensitive to complexation occurs from1500cm 1 in the ylide This band appear at lower energies compared to that found in the phosphonium salts due tothe charge delocalization present in such compound coordination of ylide through the carbon atom causes anincrease in the frequency band whereas for O coordination a lowering of the frequency band is expand The 1H NMR signals for the PCH group of complexes are shifted downfiled compared to that of the free ylides asaconsequence of the inductive effect of the metal center The reaction of dinnuclear palladium complex withbidentate ligands L phen bipy 4 mephen 5 NO2phen to prepare orthopalladated complexes in the roomtemperature single crystals of Pd phen CH2 CH PPh3 COCl TfO Pd 4 phen CH2 CH PPh3 COCl TfOsuitable for X ray crystallography were obtained which demonstrate the existence of the TfO as counter ion in thesolution The ORTEP diagram of the complexes demonstrate the orthopalladation occurring at the ph ring of thephosphine unit in endo position The palladium atoms of complexes are located in disorted square planerenvironments The analysis termogravimetry shows that the orthopalladated complexes shows that it is fairly stableup to 300 C and then degradation start The weight loss was observed in the temperature range of 300 500 C In thesecond thesis the reaction of CH3OCO CH PPh3 and mononuclear palladium complex giving the orthopalladatedcomplex C6H4CH2NH2Pd O COCH3CHPPh3 TfO the complexes were characterized by FT IR NMR The IRspectra of CH3OCO CH PPh3 show a absorption in the 1616cm 1 The IR spectra of C6H4CH2NH2Pd O COCH3CHPPh3 TfO show absorption in the 1538cm 1 The IR absorption band observed for these complexes showa lowering of frequency CO indicating coordination of the ylide oxygen for these complexes The 31P NMR spectrashows a sharp signal resonance shifted slightly up field relative to the free ylide and is again in agreement with O coordination because C coordination would result in a down field shift The 31P NMR spectra of palladiumcomplexe C6H4CH2NH2Pd O COCH3CHPPh3 TfO shows that it has transoid and cisoid isomers The Transoid ismore stable than Cisoid isomer Keyword Phosphonium salts Bidentate ligands phen bipy Orthopalladate complexes Crystallography Techniques

كاظم كرمي

شادپور ملك پور

حسين چيني فروشان، حسن حدادزاده