Cooperative H2 activation at a nickel(0)–olefin centre

Catalytic olefin hydrogenation is ubiquitous in organic synthesis. In most proposed homogeneous catalytic cycles, reactive M–H bonds are generated either by oxidative addition of H 2 to a metal centre or by deprotonation of a non-classical metal dihydrogen (M–H 2 ) intermediate. Here we provide evid...

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Bibliographic Details
Published in:Nature chemistry 2024-03, Vol.16 (3), p.417-425
Main Authors: Sansores-Paredes, María L. G., Lutz, Martin, Moret, Marc-Etienne
Format: Article
Language:English
Subjects:
639/638/263/406/939
639/638/563/934
639/638/77/885
639/638/77/888
639/638/911/406/910
Analytical Chemistry
Biochemistry
Catalysis
Catalysts
Chemical synthesis
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
Hydrogenation
Inorganic Chemistry
Isomerization
Ligands
Metals
Nickel
Organic Chemistry
Phosphine
Phosphines
Physical Chemistry
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Summary:Catalytic olefin hydrogenation is ubiquitous in organic synthesis. In most proposed homogeneous catalytic cycles, reactive M–H bonds are generated either by oxidative addition of H 2 to a metal centre or by deprotonation of a non-classical metal dihydrogen (M–H 2 ) intermediate. Here we provide evidence for an alternative H 2 -activation mechanism that instead involves direct ligand-to-ligand hydrogen transfer (LLHT) from a metal-bound H 2 molecule to a metal-coordinated olefin. An unusual pincer ligand that features two phosphine ligands and a central olefin supports the formation of a non-classical Ni–H 2 complex and the Ni(alkyl)(hydrido) product of LLHT, in rapid equilibrium with dissolved H 2 . The usefulness of this cooperative H 2 -activation mechanism for catalysis is demonstrated in the semihydrogenation of diphenylacetylene. Experimental and computational mechanistic investigations support the central role of LLHT for H 2 activation and catalytic semihydrogenation. The product distribution obtained is largely determined by the competition between ( E )–(Z) isomerization and catalyst degradation by self-hydrogenation. Activation of H 2 by a metal–olefin complex is characterized experimentally and computationally using a nickel pincer complex, showing that the reaction proceeds via a direct ligand-to-ligand hydrogen transfer mechanism. An application of this cooperative H 2 -activation mechanism is demonstrated in the nickel-catalysed semihydrogenation of diphenylacetylene.
ISSN:1755-4330
1755-4349
DOI:10.1038/s41557-023-01380-1