Catalytic C-C (C-N) bond formation and C-O bond cleavage by pincer-ligated iridium complexes
Description
TitleCatalytic C-C (C-N) bond formation and C-O bond cleavage by pincer-ligated iridium complexes
Date Created2019
Other Date2019-05 (degree)
Extent1 online resource (xxx, 388 pages) : illustrations
DescriptionSince the initial reports of catalytic alkane dehydrogenation by (tBuPCP)Ir (tBuPCP = κ3-2,6-C6H3(CH2tBu2)2) in 1996, pincer-iridium complexes have grown rapidly to include a family of derivatives. No longer limited to the original application of dehydrogenation, this new growing family shows versatile applications such as activation of X-H (X = C, N, O, Si) bonds, tandem dehydrogenation/olefin-metathesis, activation of other strong bonds, catalytic phenol-type C-O bond formation and cleavage. However, there are surprisingly few examples of dehydrogenative couplings of C−H bonds catalyzed by pincer-iridium complex, though it shows to be the ideal route for C-C bond formation. The substrates for catalytic C-O bond cleavage were also limited to alkyl phenol ethers. My PhD dissertation research aimed to discover and elucidate the mechanisms of a wider range of C-C (C-N) bond formation and C-O cleavage reactions catalyzed by pincer-ligated iridium complexes.
Chapter 2 presents the development of a tandem catalytic system for aryl-alkyl coupling. Iridium pincer complexes together with zeolites are used to convert pentylbenzene to methylnaphthalene, with hydrogen gas as the only byproduct. The utility of this method is demonstrated in the preparation of 2,6-dimethylnaphthalene, a feedstock for high performance polyesters.
Chapter 3, 4 and 5 describes the development and mechanistic investigation of dehydrogenative coupling reactions. Diaryl butadienes are obtained by homo-coupling. Cross-dehydrogenative coupling vinyl arenes with furan, thiophene, aromatics, and olefins is also demonstrated. A metalloindene complex is shown to be the key intermediate in these reactions. An intramolecular dehydrogenative coupling for the synthesis of indene and indole from vinyl arene and vinyl aniline, respectively, is further shown.
In Chapter 6, the catalytic hydrogenolysis of C-O bonds by pincer iridium complexes is shown. 1,3-diols and triols are partially deoxygenated under H2 atmosphere. An important application for this reaction is illustrated by the high yielding conversion of glycerol, an abundant side product from biofuel production, to 1,2-propanediol, a useful solvent and chemical intermediate.
Lastly, I synthesized a new pincer-iridium complex (iPrNCOP)Ir and utilized it for C-C bond formation and C-O bond cleavage.
NotePh.D.
NoteIncludes bibliographical references
Genretheses, ETD doctoral
LanguageEnglish
CollectionSchool of Graduate Studies Electronic Theses and Dissertations
Organization NameRutgers, The State University of New Jersey
RightsThe author owns the copyright to this work.
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