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New N,N,P-Ligands and Their Heterobimetallic Complexes

  • The aim of this work was to synthesize and characterize new bidentate N,N,P-ligands and their corresponding heterobimetallic complexes. These bidentate pyridylpyrimidine aminophosphine ligands were synthesized by ring closure of two different enaminones ( 3-(dimethylamino)-1-(pyridine-2-yl)-prop-2-en-1-one or 3-(dimethylamino)-1-(pyridine-2-yl)-but-2-en-1-one) with excess amount of guanidinium salts in the presence of base. The novel phosphine functionalized guanidinium salts were prepared from 2-(diphenylphosphinyl)ethylamine or 3-(diphenyl-phosphinyl)propylamine. These bidentate N,N,P-ligands contain hard and soft donor sites which allows the coordination of two different metal centers and bimetallic complexes. These bimetallic complexes can exhibit a unique behavior as a result of a cooperation between the two metal atoms. First, the gold(I) complexes of all these four different ligands were synthesized. The gold metal coordinates only to the phosphorus atom. It was proved by X-Ray crystallography technique and 31P NMR spectroscopy. Addition to the gold(I)-monometallic complexes, trans- coordinated rhodium complex of (2-amino)pyridylpyrimidine aminophosphine ligand was successfully prepared. The characterization of this complex was achieved by NMR and IR spectroscopy. Reacting the mono gold(I) complexes with the different metal salts like Pd(PhCN)2Cl2, ZnCl2, [Ru(p-cymene)Cl2] dimer gave the target heterobimetallic complexes. The second metal centers coordinated to the N,N donor site which was proved by the help of NMR spectroscopy and ESI-MS measurements. The Au(I) and Au-Zn complexes of N,N,P-ligands were examined as catalysts for the hydroamidation reaction of cyclohexene with p-toluenesulfonamide. They did not show activities under the tested conditions. Further studies are necessary to understand the catalytic activities and cooperativity between the two metal atoms. In addition, bi-and trimetallic complexes with the rhodium compound could be synthesized and tested in different organic transformations. Furthermore, the chiral hydroxyl[2.2]paracyclophane substituted with five different aminopyrimidines were accomplished. These aminopyrimidine ligands were synthesized by a cyclization reaction with hydroxyl[2.2]paracyclophane substituted enaminone and excess amount of corresponding guanidinium salts under basic conditions. In the last part of this work, kinetic studies of cyclopalladation reaction of the 2-(arylaminopyrimidin-4-yl)pyridine ligands with Pd(PhCN)2 These measurements were carried out by using UV-Vis spectroscopy. The spectral studies of cyclometallation step showed that the reaction fits a second order kinetics. In addition to this, a full kinetic investigation was performed at different temperatures and the activation parameters of complex formation were calculated.

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Author:Merve Cayir
URN (permanent link):urn:nbn:de:hbz:386-kluedo-40525
Advisor:Werner R. Thiel
Document Type:Doctoral Thesis
Language of publication:English
Publication Date:2015/04/20
Year of Publication:2015
Publishing Institute:Technische Universität Kaiserslautern
Granting Institute:Technische Universität Kaiserslautern
Acceptance Date of the Thesis:2015/04/02
Date of the Publication (Server):2015/04/21
Number of page:XII, 186
Faculties / Organisational entities:Fachbereich Chemie
DDC-Cassification:5 Naturwissenschaften und Mathematik / 540 Chemie
Licence (German):Standard gemäß KLUEDO-Leitlinien vom 13.02.2015