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Acceptorless Alcohol Dehydrogenation: OH vs NH Effect in Bifunctional NHC–Ir(III) Complexes
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-2856-5295
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-7898-317X
2018 (engelsk)Inngår i: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 37, nr 5, s. 636-644Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Bifunctional complexes bearing N-heterocyclic carbene (NHC) ligands functionalized with hydroxy or amine groups were synthesized to measure the beneficial effect of different modes of metal–ligand cooperation in the acceptorless dehydrogenation of alcohols. In comparison to complexes with an amine moiety, hydroxy-functionalized iridium catalysts showed superior activity. In contrast to alcohols, 1,4-diols underwent cyclization to give the corresponding tetrahydrofurans without involving dehydrogenation processes. Mechanistic investigations to rationalize the “OH effect” in these types of complexes have been undertaken.

sted, utgiver, år, opplag, sider
2018. Vol. 37, nr 5, s. 636-644
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-143339DOI: 10.1021/acs.organomet.7b00220ISI: 000427540100004OAI: oai:DiVA.org:su-143339DiVA, id: diva2:1098322
Forskningsfinansiär
Swedish Research CouncilKnut and Alice Wallenberg FoundationVINNOVATilgjengelig fra: 2017-05-24 Laget: 2017-05-24 Sist oppdatert: 2018-04-03bibliografisk kontrollert
Inngår i avhandling
1. Homogeneous and heterogeneous Cp*Ir(III) catalytic systems: Mechanistic studies of redox processes catalyzed by bifunctional iridium complexes, and synthesis of iridium-functionalized MOFs
Åpne denne publikasjonen i ny fane eller vindu >>Homogeneous and heterogeneous Cp*Ir(III) catalytic systems: Mechanistic studies of redox processes catalyzed by bifunctional iridium complexes, and synthesis of iridium-functionalized MOFs
2017 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

The purpose of this doctoral thesis is to investigate and develop catalytic processes mediated by iridium(III) complexes. By understanding the mechanisms, the weaknesses of the designed catalysts can be identified and be overcome in the following generation.

The thesis is composed of two general sections dedicated to the synthesis and applications of homogeneous catalysts and to the preparation of heterogeneous catalysts based on metal-organic frameworks (MOFs). After a general introduction (Chapter 1), the first part of the thesis (Chapters 2-4, and Appendix 1) covers the use of several homogeneous bifunctional [Cp*Ir(III)] catalysts in a variety of chemical transformations, as well as mechanistic studies.

Chapter 2 summarizes the studies on the N-alkylation of anilines with benzyl alcohols catalyzed by bifunctional Ir(III) complexes. Mechanistic investigations when the reactions were catalyzed by Ir(III) complexes with a hydroxy-functionalized N-heterocyclic carbene (NHC) ligand are discussed, followed by the design of a new generation of catalysts. The chapter finishes presenting the improved catalytic performance of these new complexes.   

A family of these NHC-iridium complexes was evaluated in the acceptorless dehydrogenation of alcohols, as shown in Chapter 3. The beneficial effect of a co-solvent was investigated too. Under these base-free conditions, a wide scope of alcohols was efficiently dehydrogenated in excellent yields. The unexpected higher activity of the hydroxy-containing bifunctional NHC-Ir(III) catalysts, in comparison to that of the amino-functionalized one, was investigated experimentally.

In the fourth chapter, the catalytic process presented in Chapter 3 was further explored on 1,4- and 1,5-diols, which were transformed into their corresponding tetrahydrofurans and dihydropyrans, respectively. Mechanistic investigations are also discussed.

In the second part of the thesis (Chapter 5), a Cp*Ir(III) complex was immobilized into a MOF. The heterogenization of the metal complex was achieved efficiently, reaching high ratios of functionalization. However, a change in the topology of the MOF was observed. In this chapter, the use of advanced characterization techniques such as X-ray absorption spectroscopy (XAS) and pair distribution function (PDF) analyses enabled to study a phase transformation in these materials.

sted, utgiver, år, opplag, sider
Stockholm: Department of Organic Chemistry, Stockholm University, 2017. s. 97
Emneord
catalysis, bifunctional, metal-ligand cooperation, amine alkylation, Hammett, kinetics, acceptorless alcohol dehydrogenation, MOF, transition metal, synchrotron
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-143343 (URN)978-91-7649-876-7 (ISBN)978-91-7649-877-4 (ISBN)
Disputas
2017-06-30, Magnéli Hall, Arrhenius Laboratory, Svante Arrhenius väg 16 B, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Merknad

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Submitted.

Tilgjengelig fra: 2017-06-07 Laget: 2017-05-24 Sist oppdatert: 2017-08-14bibliografisk kontrollert

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