Exploring the Reactivity of Well-defined Oxide-supported Metal­Alkyl and Alkylidyne Complexes via Surface Organometallic Chemistry

  • Aya Saidi

Student thesis: Doctoral Thesis

Abstract

Surface Organometallic Chemistry (SOMC) is an excellent approach to erase the gap between homogeneous and heterogeneous catalysis by grafting the molecular organometallic complex on various oxide surfaces, forming well-defined and single-site catalysts. This strategy allows for better characterization as well as the improvement and development of existing and new catalysts. These surface species could promote a wide range of catalytic applications (i.e., metathesis of hydrocarbons, hydrogenolysis of alkanes, and olefin polymerization reactions) depending on the metal center and its coordination sphere. In particular, the grafting of alkylated organometallic complexes of groups 4, 5, and 6 metals on the surface oxide is a thermodynamically favored reaction generally leading to strongly bonded well-defined surface species, which are highly reactive catalysts. This thesis has focused on the preparation, characterization, and catalytic investigation of different supported complexes that contain methyl, alkyl, and alkylidyne ligands. The first part compares the catalytic activity of [(≡Si−O−)W(-CH3)5] and [(≡Si-O-)Mo(≡CtBu)(-CH2tBu)2] surface species experimentally and by DFT calculations in the metathesis reactions of linear classical and functionalized olefins. Both pre-catalysts perform almost equally in the α-olefin metathesis reaction. However, in the functionalized olefin metathesis reaction, W pre-catalyst provides selective metathesis products and performs much better than Mo that gives a range of isomerization products. The second part deals with the synthesis and characterization of [(THF)2Zr(-CH3)4] and its grafting on silica support for the first time. The generated surface species [(≡Si−O−)Zr(CH3)3(THF)2] and [(≡Si−O−)2Zr(CH3)2(THF)2] are used for the conversion of CO2 and propylene oxide to cyclic propylene carbonates achieving a TON of 4227. The third part describes the first synthesis and characterization of the highly unstable homoleptic [Ti(-CH3)4] without any coordinating solvent. This complex was stabilized by grafting on SiO2-700, yielding two fully characterized surface species [(≡Si-O-)TiMe3] and [(≡Si-O-Si≡)(≡Si-O-)TiMe3], which were used in the hydrogenolysis reaction of propane and n-butane, with TONs of 419 and 578, respectively. Finally, the fourth part reports the immobilization and characterization of [TiMe2Cl2], an intermediate in the synthesis of [Ti(-CH3)4], on SiO2-700 resulting in [(≡Si-O-)TiMeCl2] and [(≡Si-O-)TiMe2Cl] surface species. These complexes reacted with a demethylating Lewis acid agent (BARF), forming the corresponding cationic Ti species [(≡Si-O-)TiMeCl]+ and [(≡Si-O-)TiCl2]+. Both neutral and cationic complexes were tested in the ethylene polymerization reaction affording linear HDPE with high molecular weights of 500,367 and 486,612 g/mol.
Date of AwardFeb 2021
Original languageEnglish (US)
Awarding Institution
  • Physical Science and Engineering
SupervisorJean-Marie Basset (Supervisor)

Keywords

  • Catalysis
  • Methyl ligand
  • Surface organometallic chemistry
  • Olefin metathesis
  • CO2 conversion
  • Hydrogenolysis of alkanes

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