Mechanistic Investigation into Copper(I) Hydride Catalyzed Formic Acid Dehydrogenation

Overview

Journal ACS Catal

Publisher American Chemical Society

Date 2024 Oct 24

PMID 39444528

Authors

Roel L M Bienenmann

Anne Olarte Loyo

Martin Lutz

Daniel L J Broere

Affiliations

Soon will be listed here.

Abstract

Copper(I) hydride complexes are typically known to react with CO to form their corresponding copper formate counterparts. However, recently it has been observed that some multinuclear copper hydrides can feature the opposite reactivity and catalyze the dehydrogenation of formic acid. Here we report the use of a multinuclear PNNP copper hydride complex as an active (pre)catalyst for this reaction. Mechanistic investigations provide insights into the catalyst resting state and the rate-determining step and identify an off-cycle species that is responsible for the unexpected substrate inhibition in this reaction.

References

Boddien A, Mellmann D, Gartner F, Jackstell R, Junge H, Dyson P . Efficient dehydrogenation of formic acid using an iron catalyst. Science. 2011; 333(6050):1733-6. DOI: 10.1126/science.1206613. View

Nakamae K, Tanaka M, Kure B, Nakajima T, Ura Y, Tanase T . A Fluxional Cu H Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO. Chemistry. 2017; 23(40):9457-9461. DOI: 10.1002/chem.201702071. View

Loges B, Boddien A, Junge H, Beller M . Controlled generation of hydrogen from formic acid amine adducts at room temperature and application in H2/O2 fuel cells. Angew Chem Int Ed Engl. 2008; 47(21):3962-5. DOI: 10.1002/anie.200705972. View

Nakajima T, Kamiryo Y, Kishimoto M, Imai K, Nakamae K, Ura Y . Synergistic Cu Catalysts for Formic Acid Dehydrogenation. J Am Chem Soc. 2019; 141(22):8732-8736. DOI: 10.1021/jacs.9b03532. View

Wyss C, Tate B, Bacsa J, Gray T, Sadighi J . Bonding and reactivity of a μ-hydrido dicopper cation. Angew Chem Int Ed Engl. 2013; 52(49):12920-3. DOI: 10.1002/anie.201306736. View

Patrick E, Bowden M, Erickson J, Bullock R, Tran B . Single-Crystal to Single-Crystal Transformations: Stepwise CO Insertions into Bridging Hydrides of [(NHC)CuH] Complexes. Angew Chem Int Ed Engl. 2023; 62(30):e202304648. DOI: 10.1002/anie.202304648. View

Nakamae K, Nakajima T, Ura Y, Kitagawa Y, Tanase T . Facially Dispersed Polyhydride Cu and Cu Clusters Comprising Apex-Truncated Supertetrahedral and Square-Face-Capped Cuboctahedral Copper Frameworks. Angew Chem Int Ed Engl. 2019; 59(6):2262-2267. DOI: 10.1002/anie.201913533. View

Guan C, Zhang D, Pan Y, Iguchi M, Ajitha M, Hu J . Dehydrogenation of Formic Acid Catalyzed by a Ruthenium Complex with an N,N'-Diimine Ligand. Inorg Chem. 2016; 56(1):438-445. DOI: 10.1021/acs.inorgchem.6b02334. View

Kar S, Rauch M, Leitus G, Ben-David Y, Milstein D . Highly Efficient Additive-Free Dehydrogenation of Neat Formic Acid. Nat Catal. 2023; 4:193-201. PMC: 7614505. DOI: 10.1038/s41929-021-00575-4. View

10.

Desnoyer A, Nicolay A, Ziegler M, Torquato N, Don Tilley T . A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes. Angew Chem Int Ed Engl. 2020; 59(31):12769-12773. DOI: 10.1002/anie.202004346. View

11.

Nakamae K, Kure B, Nakajima T, Ura Y, Tanase T . Facile insertion of carbon dioxide into Cu₂(μ-H) dinuclear units supported by tetraphosphine ligands. Chem Asian J. 2014; 9(11):3106-10. DOI: 10.1002/asia.201402900. View

12.

Zhang L, Cheng J, Hou Z . Highly efficient catalytic hydrosilylation of carbon dioxide by an N-heterocyclic carbene copper catalyst. Chem Commun (Camb). 2013; 49(42):4782-4. DOI: 10.1039/c3cc41838c. View

13.

Tran B, Neisen B, Speelman A, Gunasekara T, Wiedner E, Bullock R . Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu-H: Different Rate-Limiting Steps as a Function of Electrophilicity. Angew Chem Int Ed Engl. 2020; 59(22):8645-8653. DOI: 10.1002/anie.201916406. View

14.

Speelman A, Tran B, Erickson J, Vasiliu M, Dixon D, Bullock R . Accelerating the insertion reactions of (NHC)Cu-H remote ligand functionalization. Chem Sci. 2021; 12(34):11495-11505. PMC: 8409461. DOI: 10.1039/d1sc01911b. View

15.

Zhou W, Wei Z, Spannenberg A, Jiao H, Junge K, Junge H . Cobalt-Catalyzed Aqueous Dehydrogenation of Formic Acid. Chemistry. 2019; 25(36):8459-8464. PMC: 6618042. DOI: 10.1002/chem.201805612. View

16.

Weigend F, Ahlrichs R . Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys Chem Chem Phys. 2005; 7(18):3297-305. DOI: 10.1039/b508541a. View

17.

Marenich A, Cramer C, Truhlar D . Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J Phys Chem B. 2009; 113(18):6378-96. DOI: 10.1021/jp810292n. View

18.

Kounalis E, Lutz M, Broere D . Cooperative H Activation on Dicopper(I) Facilitated by Reversible Dearomatization of an "Expanded PNNP Pincer" Ligand. Chemistry. 2019; 25(58):13280-13284. PMC: 6856846. DOI: 10.1002/chem.201903724. View

19.

Killian L, Bienenmann R, Broere D . Quantification of the Steric Properties of 1,8-Naphthyridine-Based Ligands in Dinuclear Complexes. Organometallics. 2023; 42(1):27-37. PMC: 9832537. DOI: 10.1021/acs.organomet.2c00458. View

20.

Chai J, Head-Gordon M . Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. Phys Chem Chem Phys. 2008; 10(44):6615-20. DOI: 10.1039/b810189b. View