Visible-Light-Promoted Iridium(III)-Catalyzed Acceptorless Dehydrogenation of N-Heterocycles at Room Temperature

Overview

Journal ACS Catal

Publisher American Chemical Society

Date 2022 May 31

PMID 35633898

Authors

Carmen Mejuto

Laura Ibanez-Ibanez

Gregorio Guisado-Barrios

Jose A Mata

Affiliations

Soon will be listed here.

Abstract

An effective visible-light-promoted iridium(III)-catalyzed hydrogen production from N-heterocycles is described. A single iridium complex constitutes the photocatalytic system playing a dual task, harvesting visible-light and facilitating C-H cleavage and H formation at room temperature and without additives. The presence of a chelating C-N ligand combining a mesoionic carbene ligand along with an amido functionality in the Ir complex is essential to attain the photocatalytic transformation. Furthermore, the Ir complex is also an efficient catalyst for the thermal reverse process under mild conditions, positioning itself as a proficient candidate for liquid organic hydrogen carrier technologies (LOHCs). Mechanistic studies support a light-induced formation of H from the Ir-H intermediate as the operating mode of the iridium complex.

Citing Articles

Double Catalytic Activity Unveiled: Synthesis, Characterization, and Catalytic Applications of Iridium Complexes in Transfer Hydrogenation and Photomediated Transformations.

Blanco L, Uroz A, Gutierrez K, Cabrera S, Collado A, Aleman J ACS Catal. 2024; 14(9):6413-6422.

PMID: 38721373 PMC: 11075020. DOI: 10.1021/acscatal.4c00673.

Impact of Bidentate Pyridyl-Mesoionic Carbene Ligands: Structural, (Spectro)Electrochemical, Photophysical, and Theoretical Investigations on Ruthenium(II) Complexes.

Bens T, Kubler J, Walter R, Beerhues J, Wenger O, Sarkar B ACS Org Inorg Au. 2023; 3(4):184-198.

PMID: 37545659 PMC: 10401885. DOI: 10.1021/acsorginorgau.3c00005.

Biocatalytic and Chemo-Enzymatic Synthesis of Quinolines and 2-Quinolones by Monoamine Oxidase (MAO-N) and Horseradish Peroxidase (HRP) Biocatalysts.

Xiang H, Ferla S, Varricchio C, Brancale A, Brown N, Black G ACS Catal. 2023; 13(5):3370-3378.

PMID: 36910872 PMC: 9990064. DOI: 10.1021/acscatal.2c05902.

Visible-light-driven SAQS-catalyzed aerobic oxidative dehydrogenation of alkyl 2-phenylhydrazinecarboxylates.

Tran V, Kim H RSC Adv. 2022; 12(47):30304-30309.

PMID: 36337952 PMC: 9590590. DOI: 10.1039/d2ra05842a.

References

He K, Tan F, Zhou C, Zhou G, Yang X, Li Y . Acceptorless Dehydrogenation of N-Heterocycles by Merging Visible-Light Photoredox Catalysis and Cobalt Catalysis. Angew Chem Int Ed Engl. 2017; 56(11):3080-3084. DOI: 10.1002/anie.201612486. View

Strydom I, Guisado-Barrios G, Fernandez I, Liles D, Peris E, Bezuidenhout D . A Hemilabile and Cooperative N-Donor-Functionalized 1,2,3-Triazol-5-Ylidene Ligand for Alkyne Hydrothiolation Reactions. Chemistry. 2016; 23(6):1393-1401. DOI: 10.1002/chem.201604567. View

Bouffard J, Keitz B, Tonner R, Lavallo V, Guisado-Barrios G, Frenking G . Synthesis of Highly Stable 1,3-Diaryl-1H-1,2,3-triazol-5-ylidenes and their Applications in Ruthenium-Catalyzed Olefin Metathesis. Organometallics. 2011; 30(9):2617-2627. PMC: 3092707. DOI: 10.1021/om200272m. View

Deraedt C, Ye R, Ralston W, Toste F, Somorjai G . Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N-Heterocycles. J Am Chem Soc. 2017; 139(49):18084-18092. DOI: 10.1021/jacs.7b10768. View

Yin Q, Oestreich M . Photocatalysis Enabling Acceptorless Dehydrogenation of Benzofused Saturated Rings at Room Temperature. Angew Chem Int Ed Engl. 2017; 56(27):7716-7718. DOI: 10.1002/anie.201703536. View

Yamaguchi R, Ikeda C, Takahashi Y, Fujita K . Homogeneous catalytic system for reversible dehydrogenation-hydrogenation reactions of nitrogen heterocycles with reversible interconversion of catalytic species. J Am Chem Soc. 2009; 131(24):8410-2. DOI: 10.1021/ja9022623. View

Zheng M, Shi J, Yuan T, Wang X . Metal-Free Dehydrogenation of N-Heterocycles by Ternary h-BCN Nanosheets with Visible Light. Angew Chem Int Ed Engl. 2018; 57(19):5487-5491. DOI: 10.1002/anie.201800319. View

Petronilho A, Rahman M, Woods J, Al-Sayyed H, Muller-Bunz H, MacElroy J . Photolytic water oxidation catalyzed by a molecular carbene iridium complex. Dalton Trans. 2012; 41(42):13074-80. DOI: 10.1039/c2dt30403a. View

Wu J, Talwar D, Johnston S, Yan M, Xiao J . Acceptorless dehydrogenation of nitrogen heterocycles with a versatile iridium catalyst. Angew Chem Int Ed Engl. 2013; 52(27):6983-7. DOI: 10.1002/anie.201300292. View

10.

Crabtree R . Homogeneous Transition Metal Catalysis of Acceptorless Dehydrogenative Alcohol Oxidation: Applications in Hydrogen Storage and to Heterocycle Synthesis. Chem Rev. 2017; 117(13):9228-9246. DOI: 10.1021/acs.chemrev.6b00556. View

11.

Wang S, Huang H, Bruneau C, Fischmeister C . Iridium-Catalyzed Hydrogenation and Dehydrogenation of N-Heterocycles in Water under Mild Conditions. ChemSusChem. 2019; 12(11):2350-2354. DOI: 10.1002/cssc.201900626. View

12.

Schultz D, Yoon T . Solar synthesis: prospects in visible light photocatalysis. Science. 2014; 343(6174):1239176. PMC: 4547527. DOI: 10.1126/science.1239176. View

13.

Chambers M, Kurtz D, Pitman C, Brennaman M, Miller A . Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism. J Am Chem Soc. 2016; 138(41):13509-13512. DOI: 10.1021/jacs.6b08701. View

14.

Cheung K, Sarkar S, Gevorgyan V . Visible Light-Induced Transition Metal Catalysis. Chem Rev. 2021; 122(2):1543-1625. PMC: 9017709. DOI: 10.1021/acs.chemrev.1c00403. View

15.

Guisado-Barrios G, Soleilhavoup M, Bertrand G . 1 H-1,2,3-Triazol-5-ylidenes: Readily Available Mesoionic Carbenes. Acc Chem Res. 2018; 51(12):3236-3244. DOI: 10.1021/acs.accounts.8b00480. View

16.

Sypaseuth F, Matlachowski C, Weber M, Schwalbe M, Tzschucke C . Electrocatalytic carbon dioxide reduction by using cationic pentamethylcyclopentadienyl-iridium complexes with unsymmetrically substituted bipyridine ligands. Chemistry. 2015; 21(17):6564-71. DOI: 10.1002/chem.201404367. View

17.

Maity R, Sarkar B . Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes. JACS Au. 2022; 2(1):22-57. PMC: 8790748. DOI: 10.1021/jacsau.1c00338. View

18.

Guisado-Barrios G, Bouffard J, Donnadieu B, Bertrand G . Crystalline 1H-1,2,3-triazol-5-ylidenes: new stable mesoionic carbenes (MICs). Angew Chem Int Ed Engl. 2010; 49(28):4759-62. PMC: 3131155. DOI: 10.1002/anie.201001864. View

19.

Kato S, Saga Y, Kojima M, Fuse H, Matsunaga S, Fukatsu A . Hybrid Catalysis Enabling Room-Temperature Hydrogen Gas Release from N-Heterocycles and Tetrahydronaphthalenes. J Am Chem Soc. 2017; 139(6):2204-2207. DOI: 10.1021/jacs.7b00253. View

20.

Park Y, Kim S, Tian L, Zhong H, Scholes G, Chirik P . Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen. Nat Chem. 2021; 13(10):969-976. DOI: 10.1038/s41557-021-00732-z. View