سنتز و شناسايي كمپلكس هاي اورتوپالاديت فسفر ايليد ﴿dppe﴾ و آمين نوع دوم ﴿n-بنزيل-tert-بوتيل آمين﴾ و بررسي واكنش جايگيري تك مولكولي و دو مولكولي دي متيل استيلن دي كربوكسيلات در پيوند Pd-C

چكيده انگليسي :

Synthesis and Characterization of Orthopalladated Complexes Phosphorus Ylide dppe and Second Amin n butyl benzyl amin and Insertion of One and Two Molecules of DMAD Into The Pd C Bond Samira Rezvani Sichani sr chemistry26@yahoo com Date of Submission 2012 2 25 Department of Chemistry Isfahan University of Technology Isfahan 84156 83111 Iran Degree M Sc Language Farsi Supervisor Kazem Karami Karmi@cc iut ac irAbstract In this thesis orthometalated complexes have been synthesized The ortho palladated complexes Pd C6H4CH2NH t Bu X 2 can be prepared by refluxing equimolecular amounts of Pd OAc 2 and C6H5CH2NH t Bu in benzene for 24 h in 50 c followed by addition of NaX X Cl Br in MeOH in this stage of the reaction Brand Cl will be replaced with acetate bridge The halogeno bridges in dimeric ortho palladated complexes containingsecondary aryl alkylamines are easily cleaved by various neutral ligands including sym Collidine PPh3 to affordmononuclear metallacycles In the second part the 1 2 insertion reaction have been done withDimethylacethylenedicarboxylate in the room temperature also 1 4 insertion reaction have been done by refluxingPd C with Dimethylacethylenedicarboxylate In aceton and in 50 c The complexes were chractrized by FT IR NMR and X ray diffraction study of Pd C6H4CH2NH t Bu sym Collidine Br X ray datas shows distortion squareplanar structure for this complexe 15 protones of the PPh3 group in the Pd C6H4CH2NH t Bu PPh3 Cl havebeen detected clearly in 1H NMR as two multiplied band that refers to 9 protones of meta and para in 7 4 7 52 ppm and 6 protones of orto groups in 7 59 7 64 ppm 31P 1H NMR of this complex show that thiscomplex may have two isomer In other part phosphorus ylide NO2BdppeY has been synthesized through theformation of phosphonium salt and dihydrogenation followed by the reaction of Pd OAc 2 and the dinuclearcomplexes Pd R NO2BdppeY 2 R OAc Cl have been prepared Then monomer complexes were prepared byusing of 2 1 ratio of neutral ligands PPh3 2 4 6 tri methylprydine and dinuclear complex in CH2Cl2 Thecomplexes were chracterized by FT IR NMR UV Vis and X ray diffraction study of NO2BdppeY Thedisappearance of peak in 2150 cm 1 in inserted complexes shows acethylene group in dimethylacethylenedicarboxylate converts to ethylene group in complex In The 1H NMR of dimeric orthopalladated complexes thepresence of one series of band on each spectrum can be originated from the presence of only trans isomer as a resultof the orthopalladated of n benzyl tert buthylamine The Single crystals of Pd Br Me3Py NH t Bu CH2C6H4 suitable for X ray crystallography were obtained Although the orthopalladated complex remarkably warped theenvironment around the Pd is planar 1H NMR of the PdNH t Bu CH2C6H4 Cl PPh3 and Pd Br Me3Py NH t Bu CH2C6H4 proves the Anisotropy effect of triphenylphosphin and 2 4 6 trimethylprydine rings on H6 of thesecomplexes and have been shifted to lower field or the shielding In the 31P 1H NMR spectra of all ylidecomplexes the presence of two isomer of C P coordination major isomer and P O coordination minor isomer have been confirmed The FT IR spectra of all complexes show a strong absorption in the range of 1582 1621 cm 1 which have been shifted to higher frequency with respect to the parent ylid meaning that the ylid is C bonded to thepalladium center that refers to major isomer C P coordination The X ray crystallography of NO2BdppeY showsthat the terminal group of PPh2 has converted to O PPh2 consequently in the 31P 1H NMR of the somecomplexes the C P coordination products with O PPh2 group have been seen Keyword Cycloopalladated complex n benzyl tert buthylamine Dimethylacethylenedicarboxylate ligands Insertion reaction

رضواني سيچاني، سميرا

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