Synthesis Characterization And Reactivity Of The Half Sandwich Ruthenium Ii Hydride Complexes Of 135 Triaza 7 Phosphaadamantane

Author : Van Hung Mai
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (124 download)

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Download or read book Half-sandwich Complexes of Ruthenium Supported by N-Heterocyclic Carbene Ligands written by Van Hung Mai and published by . This book was released on 2017 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis presents the preparation and catalytic reactivity of novel half-sandwich ruthenium complexes supported by N-Heterocyclic Carbene (NHC) ligands. The cationic half-sandwich ruthenium complexes [Cp(IPr)Ru(CH3CN)2]+ show interesting reactivities toward the transfer hydrogenation of different unsaturated substrates, such as ketones, olefins, N-heterocycles, and nitriles. Kinetic studies disclose that a neutral trishydride ruthenium complex is actually involved in the catalytic cycle, playing the role as a resting state. Further investigations on the sub-class of trishydride ruthenium complexes bearing NHC ligands (Cp'(NHC)RuH3) reveal that these complexes have an unusual and great catalytic performance toward the hydrodefluorination (HDF) of fluorinated aromatic and aliphatic compounds. The combined kinetic studies, cross-over experiments and rate law analysis suggest an unusual mechanistic pathway for the Cp*(IPr)RuH3 catalyzed HDF. This study is one of the rare examples where isopropanol is employed as a reducing agent for the metal-mediated HDF reaction. A class of silyl dihydride ruthenium complexes, derived from Cp(IPr)RuH3 are prepared. These silyl hydrido derivatives are great compounds for the study of the inter ligand hypervalent interaction (IHI), an interesting phenomenon for many non-classical silane complexes. This study also suggests that the replacement of phosphines by their isolobally analogous NHC ligands result in stronger IHI interactions in the corresponding compounds. Another type of non-classical interaction was systematically scrutinized in a ii series of new cationic and neutral silane sigma complexes of ruthenium bearing different silyl moieties. These new NHC-supported ruthenium complexes allow for direct comparation with the known phosphine analogues, which reveals interplay of steric and electronic factors on the extent of Si-H complexation to metal and the extent of additional interligand interactions between Ru-Cl and chlorosilane ligand. Finally, new trishydride ruthenium complexes bearing NHC ligands (Cp'(NHC)RuH3) catalyze the H/D exchange reaction of various N-heterocycle substrates; their catalytic performance can be considered as one of the mildest, and most efficient approaches.