Towards Supported Nitrogen Containing Fragments on Silica Surface for Catalytic Applications
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Maha Aljuhani - Final Dissertation
Type
DissertationAuthors
Aljuhani, Maha A.
Advisors
Basset, Jean-Marie
Committee members
Huang, Kuo-Wei
Saikaly, Pascal

Astruc, Didier
Program
Chemical ScienceKAUST Department
Physical Science and Engineering (PSE) DivisionDate
2019-09Embargo End Date
2020-11-17Permanent link to this record
http://hdl.handle.net/10754/660092
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At the time of archiving, the student author of this dissertation opted to temporarily restrict access to it. The full text of this dissertation became available to the public after the expiration of the embargo on 2020-11-17.Abstract
This thesis shed lights on metal-nitrogen organometallic fragments supported on silica surface for catalytic applications. It Focuses on group IV and V metal transition as a well-defined single-site catalysts, specifically titanium, hafnium, and tantalum to utilize them in the development of selective heterogeneous catalysis for imine metathesis, hydroamination and hydroaminoalkylation of olefins and alkynes. Developing new metal-nitrogen containing fragments by using easily available and abundant precursors which is silica SiO2 and metal amides complexes. Here, we describe metal fragments starting with hafnium-nitrogen fragment. All the catalysts were prepared by reacting homoleptic metal amido of group IV and V with partially dehydroxylated silica. In most cases the resulting surface amido is monopodal and leads to well defined single site catalysts precursors. In particular with Hf we have isolated hafniaaziridine 2.1 [(≡Si-O-)Hf(η2-MeNCH2)(η1-NMe2)(η1-HNMe2)], imido, and amido fragments 2.3 [(≡Si-O-)Hf(=NMe)(η1-NMe2)], and two intermediates the five-membered ring 2.2 [≡Si-O-Hf(HNMe2)(η2-NMeCH2CH(C6H13)CH2)(NMe2)] and 2.4 [(≡Si-O-)Hf(=NCH2Ar) (η1-NMe2)]. For tantalum 3.1 [(≡Si-O-)Ta=NtBu)(η1-NMeEt)2]; we have isolated two intermediates after treating 3.1 catalyst with aniline substrate lead to isolating 3.3 [(≡Si-O-)Ta(η1σ-NEtMe)2(η1σ-NHtBu)(NHC6H10)], and upon treating with 1-octyne lead to isolating 3.2 [(≡Si-O-)Ta(η1σ-NEtMe)2(η2-NtBuC=CC7H13)]. For titanium-nitrogen fragments, we isolated on silica SiO2-200 4.1 [(≡Si-O2-)Ti(NMe2)2 (η1-HNMe2)] and on SiO2-700 the titaniaaziridine 4.2a [≡Si-O-Ti(NMe2)3] 4.2b, [(≡Si-O-)Ti(η2-MeNCH2)(η1-NMe2)(η1-HNMe2)], the imido, and amido fragments 4.4 [(≡Si-O-)Ti(=NMe)(η1-NMe2)], and the five-membered ring intermediate 4.3 [≡Si-O-Ti(HNMe2)(η2-NMeCH2CH(C6H13)CH2)(NMe2)]. Research in this area has led to isolating several intermediates containing nitrogen fragments, this is the strength of surface organometallic chemistry which allows a deeper understanding of catalytic phenomena which could not be approached either in homogeneous catalysis or in classical heterogeneous catalysis. A molecular level characterization of the surface nitrogen containing fragments have been characterized by SOMC tools such as FTIR and EXAFS spectroscopy, elemental analysis, solid-state single and multiple quantum NMR, advanced DNP-SENS and DFT. A catalytic cycle was proposed based not only on the isolation of intermediates but also based on DFT calculations.Citation
Aljuhani, M. A. (2019). Towards Supported Nitrogen Containing Fragments on Silica Surface for Catalytic Applications. KAUST Research Repository. https://doi.org/10.25781/KAUST-3Z199ae974a485f413a2113503eed53cd6c53
10.25781/KAUST-3Z199