Pincer Platinum(II) Hydrides: High Stability Imparted by Donor-Flexible Pyridylidene Amide Ligands and Evidence for Adduct Formation before Protonation.

Bukvic, Alexander J; Kesselring, Vera; Aeschlimann, Michael; Albrecht, Martin (2023). Pincer Platinum(II) Hydrides: High Stability Imparted by Donor-Flexible Pyridylidene Amide Ligands and Evidence for Adduct Formation before Protonation. Inorganic chemistry, 62(6), pp. 2905-2912. American Chemical Society 10.1021/acs.inorgchem.2c04363

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Donor-flexible ligands are an emerging class of noninnocent ligands. Their ability to adapt their donating strength toward a metal center has had numerous catalytic advantages yet has never been utilized to stabilize and isolate intermediate complexes within these processes. We demonstrate through the use of a pincer ligand containing two donor-flexible pyridylidene amide (PYA) arms in coordination with platinum(II) that this ligand adaptability revealed remarkably stable hydride and formate complexes. These are typically fleeting catalytic intermediates within formic acid dehydrogenation and CO2 hydrogenation catalytic cycles. The PYA platinum hydride complexes are indefinitely stable in air, while formate complexes show no sign of β-hydrogen elimination. This robustness allowed us to investigate hydride protonation as a seemingly simple reaction, though in-depth kinetic analysis reveals a pre-equilibrium step prior to platinum hydride protonation. This initial step has been attributed to adduct formation and is slower than the protonation, and therefore a relevant aspect when designing catalytic cycles for hydrogen release and its microscopic reverse, viz., hydrogen uptake.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Bukvic, Alexander James, Kesselring, Vera Maria, Albrecht, Martin

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
000 Computer science, knowledge & systems

ISSN:

0020-1669

Publisher:

American Chemical Society

Language:

English

Submitter:

Pubmed Import

Date Deposited:

01 Feb 2023 09:32

Last Modified:

14 Feb 2023 00:16

Publisher DOI:

10.1021/acs.inorgchem.2c04363

PubMed ID:

36719961

BORIS DOI:

URI:

https://boris.unibe.ch/id/eprint/178188

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