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Record Nr. |
UNINA9910254152703321 |
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Autore |
Cheng Gui-Juan |
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Titolo |
Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods / / by Gui-Juan Cheng |
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Pubbl/distr/stampa |
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Singapore : , : Springer Singapore : , : Imprint : Springer, , 2017 |
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ISBN |
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Edizione |
[1st ed. 2017.] |
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Descrizione fisica |
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1 online resource (XVII, 126 p. 95 illus., 77 illus. in color.) |
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Collana |
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Springer Theses, Recognizing Outstanding Ph.D. Research, , 2190-5053 |
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Disciplina |
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Soggetti |
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Chemistry, Physical and theoretical |
Organometallic chemistry |
Catalysis |
Mass spectrometry |
Theoretical and Computational Chemistry |
Organometallic Chemistry |
Mass Spectrometry |
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Lingua di pubblicazione |
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Formato |
Materiale a stampa |
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Livello bibliografico |
Monografia |
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Note generali |
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"Doctoral Thesis accepted by Peking University, Beijing, China." -- title page. |
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Nota di bibliografia |
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Includes bibliographical references at the end of each chapters. |
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Nota di contenuto |
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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. |
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Sommario/riassunto |
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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 |
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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. |
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