04592nam 22006375 450 991025415270332120200705235148.0981-10-4521-610.1007/978-981-10-4521-9(CKB)3710000001404737(DE-He213)978-981-10-4521-9(MiAaPQ)EBC4873431(PPN)202991881(EXLCZ)99371000000140473720170607d2017 u| 0engurnn|008mamaatxtrdacontentcrdamediacrrdacarrierMechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods /by Gui-Juan Cheng1st ed. 2017.Singapore :Springer Singapore :Imprint: Springer,2017.1 online resource (XVII, 126 p. 95 illus., 77 illus. in color.) Springer Theses, Recognizing Outstanding Ph.D. Research,2190-5053"Doctoral Thesis accepted by Peking University, Beijing, China." -- title page.981-10-4520-8 Includes bibliographical references at the end of each chapters.Introduction -- Mechanistic Studies on meta-C-H Activation Reaction -- Mechanistic Studies on MPAA-assisted meta-C-H Activation Reaction -- Mechanistic Studies on MPAA-assisted Asymmetric C-H Activation Reaction -- Mechanistic Studies on Cu-catalyzed sp3 C-H Cross-Dehydrogenative-Coupling Reaction -- Conclusions and Outlook.This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.Springer Theses, Recognizing Outstanding Ph.D. Research,2190-5053Chemistry, Physical and theoreticalOrganometallic chemistryCatalysisMass spectrometryTheoretical and Computational Chemistryhttps://scigraph.springernature.com/ontologies/product-market-codes/C25007Organometallic Chemistryhttps://scigraph.springernature.com/ontologies/product-market-codes/C19020Catalysishttps://scigraph.springernature.com/ontologies/product-market-codes/C29000Mass Spectrometryhttps://scigraph.springernature.com/ontologies/product-market-codes/C11010Chemistry, Physical and theoretical.Organometallic chemistry.Catalysis.Mass spectrometry.Theoretical and Computational Chemistry.Organometallic Chemistry.Catalysis.Mass Spectrometry.547.2Cheng Gui-Juanauthttp://id.loc.gov/vocabulary/relators/aut767359MiAaPQMiAaPQMiAaPQBOOK9910254152703321Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods1562242UNINA