ETD system

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Tesi etd-02192020-223622


Thesis type
Tesi di dottorato di ricerca
Author
BARTALUCCI, NICCOLO'
URN
etd-02192020-223622
Title
Exploiting the Potentiality of High Valent Transition Metal Halides in Organic Synthesis
Settore scientifico disciplinare
CHIM/03
Corso di studi
SCIENZE CHIMICHE E DEI MATERIALI
Supervisors
tutor Prof. Marchetti, Fabio
Parole chiave
  • Metal
  • Halides
  • Niobium
  • Tantalum
  • Molybdenum
  • Tungsten
  • High
  • Transition
  • Valent
Data inizio appello
24/02/2020;
Consultabilità
Parziale
Data di rilascio
24/02/2023
Riassunto analitico
Halides of group 5 and 6 transition metals in a +5 or +6 oxidation state (high valent metal halides, HVMH) are strong Lewis acids that can also exploit oxidizing power and halogenating ability, thus constituting potential mediators in various organic transformations. In the framework of our interest in the chemistry of HVMH with different organic functionalities, we have investigated the reactions with compounds bearing unsaturated C-N or C-O bonds. Activation products, like quinoxalinium and imidazolium salts, were obtained from the reactions of HVMH with a-diimines, as a result of intra-/inter-molecular couplings. Also, rare coordination complexes were isolated and characterized, including the first examples of high valent metal fluoride adducts with a-diimines. Unprecedented, “non-classical” coordination compounds were afforded from NbX5 (X = Cl, Br) and isocyanides. Furthermore, clean CO release at room temperature was observed for the first time from tertiary a-phenylcarboxylic acids upon interaction with HVMH, resulting in either the isolation of stable carbocation salts, or their conversion into more stable hydrocarbons.
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