- Fundamental reactivity of the Metal-Carbon bond in cyclometalated PNC-complexes
- Award date
- 28 September 2016
- Number of pages
- Document type
- PhD thesis
- Faculty of Science (FNWI)
- Van 't Hoff Institute for Molecular Sciences (HIMS)
The activation of C-H bonds by transition metals and the reactivity of the corresponding metal-carbon bond are interesting research topics form different point of views. Catalytic C-H bond functionalization has emerged as a highly active research area for the development of green construction of Carbon-Carbon and Carbon-heteroatom bonds. Fundamental knowledge on the mechanism of stoichiometric activation and functionalization of C-H bonds can lead to improved catalytic reactions. Furthermore, the reversible nature of C-H activation could account for metal-ligand cooperativity.
This thesis describes the coordination chemistry and reactivity of P,N,C-ligands ( 2-(di-tert-butylphosphinomethyl)-2-phenyl-pyridine and 2-(di-tert-butylphosphinito)-6-phenyl-pyridine) in Rh(I) and Ni(II) complexes. The strong P,N-chelation to the metal brings the ortho-C-H of a flanking phenyl ring in proximity of the metal, which results in facile C-H activation in both metal complexes. Although the Metal-Carbon bond is easily formed, it is still reactive in presence of acids and strong electrophiles. Application of such cyclometalated complexes in cooperative base-free dehydrogenation of formic acid is reported. Another topic of this thesis is the isolation of complexes with Metal-(C-H) interactions, which are generally considered to precede the C-H activation step. Furthermore, the reactivity of the Metal-Carbon bond with respect to formation of Carbon-Carbon bonds is described.
- For copyright reasons, the cover of the thesis has been placed under a permanent embargo and is not included in this download version of the thesis.
Thesis (Embargo up to and including 28 September 2018)
1. C-H activation, C-C bond formation and bifunctional catalysis: a general introduction (Embargo up to and including 28 September 2018)
5. Oxidation-induced C(sp²)-C(sp³) bond formation from cyclometalated Ni(II) complexes (Embargo up to and including 28 September 2018)
If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library, or send a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible.