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悉尼有机化学论文-二茂铁亚胺环钯化合物的合成、表征及其催化反应-Cyclopalladated Ferrocenylimines Complexes: Synthesis, Characterization and Application in C-C and C-N Coupling Reactions-In this thesis, the synthesis, characterization and crystal structures of a series of newpyridine adducts, tricyclohexylphosphine adducts and monophosphinobiaryl ligand（DCPAB, DCPB） adducts of dimeric cyclopalladated ferrocenylimines were reported.

These complexes have been successfully used in palladium-catalyzed C-C and C-Nbond forming reactions of aryl bromides and aryl chlorides.1. Five new pyridine-cyclopalladated ferrocenylimine complexes 1-5 have been easilyprepared （Schemel） and well characterized by elemental analysis, ESI-MS, 1H NMRand IR spectra.

Their detailed structures are determined by single-crystal X-rayanalysis. To the best of our knowledge, the crystal structures of all monomeric imineand amine-based palladacycles indicate that, in the solid state, the trans isomercrystallizes preferentially. Surprisingly, the single crystal X-ray analysis of complex 2and 5 revealed cis-configuration of coordinated pyridine to the imino nitrogen in thesolid state, while 1, 3 and 4 are trans complexes. These complexes were found to beefficient for the Suzuki reaction of aryl bromides with phenylboronic acid.  https://www.51lunwen.org/australiathesis/  

Typically,using 0.2 mol% of 1 in the presence of 1.5 equivalent of K2CO3 as base in toluene at100℃could provide the coupled products in good to excellent yields.2. A series of new tricyclohexylphosphine（PCy3）-cyclopalladated ferrocenyliminescomplexes 6-11 have been easily synthesized （Scheme 2）. The synthesis andcharacterization of a new 1,1’-bisferrocenylimine [{（η5-C5H4）-CH=NCy}2Fe] 12 and its monocyclopalladated derivative 14 were also reported （Scheme 3）. The compound14 was found to be [PdCl{[（η5-C5H4）-CHO]Fe[（η5-C5H3）-CH=NCy]}（PCy3）], whichwas obtained from the reaction of 12 with equimolar amounts of Li2PdCl4/NaOAc inmethanol at room temperature and subsequent treatment of the resulting product withtricyclohexylphosphine （PCy3）. The detailed structures of seven new palladacycleshave been determined by single-crystal X-ray analysis. The use of these palladacycles6-10 and 14 as catalysts for Suzuki and Heck reactions was examined.

They werefound to be very efficient for the Suzuki reaction of aryl chlorides with phenylboronicacid. Typically, using 0.1 mol% of catalyst in the presence of 1.5 equivalent ofCs2CO3 as base in dioxane at 100℃provided coupled products in excellent yields.These complexes also displayed good activity in the Heck reaction of a range of arylbromides with acrylic acid ethyl ester although they were not particularly useful forthe activation of aryl chlorides.3. One-pot synthesis of symmetrical biaryls via the coupling of bis（pinacolato）-diboron with aryl chlorides catalyzed by tricyclohexylphosphine-cyclopalladatedferrocenylimine complexes has been described （Scheme 4）. These complexes werehighly effective catalysts and the typical catalytic loadings were 0.5-1mol%, whichwere rather low compared to the value of 4 mol% in the PdCl2（dppf） catalyzedcoupling of aryl bromides. The corresponding symmetrical biaryls were isolated in good to high yields.4. A series of new monophosphinobiaryl ligand （DCPB and DCPAB）-cyclopalladatedferrocenylimines complexes 16-25 have been easily synthesized （Scheme 5）.

Thedetailed structures of six new palladacycles 16-17, 20, 22-23, 25 have beendetermined by 本论文由英语论文网提供整理，提供论文代写，英语论文代写，代写论文，代写英语论文，代写留学生论文，代写英文论文，留学生论文代写相关核心关键词搜索。