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Ruthenium, Iridium Metal Complexes Synthesis And Its Application In Organic Reactions

Posted on:2013-01-28Degree:MasterType:Thesis
Country:ChinaCandidate:L H CaiFull Text:PDF
GTID:2241330395950697Subject:Chemical Engineering
Abstract/Summary:PDF Full Text Request
Transfer Hydrogenation of C=O and C=N groups is an important reaction for which NHC metal complexes have demonstrated particularly good activity. The C=O case has been most extensively studied, leading to important applications such as racemization of chiral alcohols and asymmetric reductions.Part1:A smally family of available ruthenium or iridium complexes was used in racemization of (R)-1-phenylethanol to study the influence on the ligands coordinated to metal center. Moreover, all these complexes were applied to the DKR of1-phenylethanol to check the suitability of the catalysts to the enzyme-435.[Ru(cymene)Cl2]2was then chosen out to catalyze the DKR of various sec-alcohols under the relatively mild condition with good performance. Besides that, the mechanism for racemization of sec-alcohols by [Ru(cymene)Cl2]2was proposed. Ruthenium-cymene chloride complexes bearing different ligands were calculated the barrier that ligands dissociation required to support the proposed mechanism.Part2:Four single-nuclear iridium compounds with acetyl functionalized N-heterocyclic carbine were prepared successfully and characterized by1H NMR and13C NMR.2-4a,2-4d and2-5was used as the catalyst in transfer hydrogenation of acetophenone to investigate the influence of the acetyl group. The transfer hydrogenation of C=O and C=N groups were also carried on used2-4a with excellent performance.2-4c was selected to use as the catalyst precursor in N-alkylation of amines with good performance.
Keywords/Search Tags:Transfer Hydrogenation, Dynamic Kinetic Resolution, Rutheniumcomplexes, N-heterocyclic carbenes, acetyl group
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