Radical-like Reactivity for Dihydrogen Activation by Coinage Metal-aluminyl Complexes: Computational Evidence Inspired by Experimental Main Group Chemistry

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2023 Feb 9

PMID 36755722

Authors

Diego Sorbelli

Leonardo Belpassi

Paola Belanzoni

Affiliations

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Abstract

The computational study of an unprecedented reactivity of coinage metal-aluminyl complexes with dihydrogen is reported. In close resemblance to group 14 dimetallenes and dimetallynes, the complexes are predicted to activate H under mild conditions. Two different reaction pathways are found disclosing a common driving force, , the nucleophilic behavior of the electron-sharing M-Al (M = Cu, Ag, Au) bond, which enables a cooperative and diradical-like mechanism. This mode of chemical reactivity emerges as a new paradigm for dihydrogen activation and calls for experimental feedback.

References

Villegas-Escobar N, Toro-Labbe A, Schaefer 3rd H . Contrasting the Mechanism of H Activation by Monomeric and Potassium-Stabilized Dimeric Al Complexes: Do Potassium Atoms Exert any Cooperative Effect?. Chemistry. 2021; 27(69):17369-17378. DOI: 10.1002/chem.202103082. View

Xu M, Jupp A, Qu Z, Stephan D . Alkali Metal Species in the Reversible Activation of H. Angew Chem Int Ed Engl. 2018; 57(34):11050-11054. DOI: 10.1002/anie.201806849. View

Michalak A, Mitoraj M, Ziegler T . Bond orbitals from chemical valence theory. J Phys Chem A. 2008; 112(9):1933-9. DOI: 10.1021/jp075460u. View

Charles 3rd R, Brewster T . H and carbon-heteroatom bond activation mediated by polarized heterobimetallic complexes. Coord Chem Rev. 2022; 433. PMC: 9004596. DOI: 10.1016/j.ccr.2020.213765. View

McManus C, Hicks J, Cui X, Zhao L, Frenking G, Goicoechea J . Coinage metal aluminyl complexes: probing regiochemistry and mechanism in the insertion and reduction of carbon dioxide. Chem Sci. 2021; 12(40):13458-13468. PMC: 8528051. DOI: 10.1039/d1sc04676d. View

Bickelhaupt F, Houk K . Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model. Angew Chem Int Ed Engl. 2017; 56(34):10070-10086. PMC: 5601271. DOI: 10.1002/anie.201701486. View

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

Sorbelli D, Rossi E, Havenith R, Klein J, Belpassi L, Belanzoni P . Gold-Aluminyl and Gold-Diarylboryl Complexes: Bonding and Reactivity with Carbon Dioxide. Inorg Chem. 2022; 61(19):7327-7337. PMC: 9115750. DOI: 10.1021/acs.inorgchem.2c00174. View

Devillard M, Declercq R, Nicolas E, Ehlers A, Backs J, Saffon-Merceron N . A Significant but Constrained Geometry Pt→Al Interaction: Fixation of CO2 and CS2, Activation of H2 and PhCONH2. J Am Chem Soc. 2016; 138(14):4917-26. DOI: 10.1021/jacs.6b01320. View

10.

Klein J, Mandal D, Ching W, Mallick D, Que Jr L, Shaik S . Privileged Role of Thiolate as the Axial Ligand in Hydrogen Atom Transfer Reactions by Oxoiron(IV) Complexes in Shaping the Potential Energy Surface and Inducing Significant H-Atom Tunneling. J Am Chem Soc. 2017; 139(51):18705-18713. DOI: 10.1021/jacs.7b11300. View

11.

Bistoni G, Rampino S, Tarantelli F, Belpassi L . Charge-displacement analysis via natural orbitals for chemical valence: charge transfer effects in coordination chemistry. J Chem Phys. 2015; 142(8):084112. DOI: 10.1063/1.4908537. View

12.

Spikes G, Fettinger J, Power P . Facile activation of dihydrogen by an unsaturated heavier main group compound. J Am Chem Soc. 2005; 127(35):12232-3. DOI: 10.1021/ja053247a. View

13.

Meisner J, Kastner J . Atom Tunneling in Chemistry. Angew Chem Int Ed Engl. 2016; 55(18):5400-13. DOI: 10.1002/anie.201511028. View

14.

Bamford K, Qu Z, Stephan D . Activation of H and EtSiH by the Borinium Cation [MesB]: Avenues to Cations [MesB(μ-H)(μ-Mes)BMes] and [HB(μ-H)(μ-Mes)B(μ-Mes)(μ-H)BH]. J Am Chem Soc. 2019; 141(15):6180-6184. DOI: 10.1021/jacs.9b02510. View

15.

Sorbelli D, Belpassi L, Belanzoni P . What Singles out Aluminyl Anions? A Comparative Computational Study of the Carbon Dioxide Insertion Reaction in Gold-Aluminyl, -Gallyl, and -Indyl Complexes. Inorg Chem. 2022; 61(3):1704-1716. PMC: 8790757. DOI: 10.1021/acs.inorgchem.1c03579. View

16.

Li J, Schenk C, Goedecke C, Frenking G, Jones C . A digermyne with a Ge-Ge single bond that activates dihydrogen in the solid state. J Am Chem Soc. 2011; 133(46):18622-5. DOI: 10.1021/ja209215a. View

17.

Mitoraj M, Michalak A . Natural orbitals for chemical valence as descriptors of chemical bonding in transition metal complexes. J Mol Model. 2006; 13(2):347-55. DOI: 10.1007/s00894-006-0149-4. View

18.

Fernandez I, Bickelhaupt F . The activation strain model and molecular orbital theory: understanding and designing chemical reactions. Chem Soc Rev. 2014; 43(14):4953-67. DOI: 10.1039/c4cs00055b. View

19.

Grimme S, Antony J, Ehrlich S, Krieg H . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. 2010; 132(15):154104. DOI: 10.1063/1.3382344. View

20.

Li J, Hermann M, Frenking G, Jones C . The facile reduction of carbon dioxide to carbon monoxide with an amido-digermyne. Angew Chem Int Ed Engl. 2012; 51(34):8611-4. DOI: 10.1002/anie.201203607. View