Catalytic Hydrogenation of a Ruthenium Carbonyl to Formyl Enabled by Metal–Ligand Cooperation

Smith, Allison M.; Fernández, Sergio; Tereniak, Stephen J.; Ahmad, Shahbaz; Kumar, Abhishek; Chen, Chun-Hsing; Hazari, Nilay; Ertem, Mehmed Z.; Miller, Alexander J. M.

doi:10.1021/acscatal.5c03137

Catalytic Hydrogenation of a Ruthenium Carbonyl to Formyl Enabled by Metal–Ligand Cooperation

Journal Article · Tue Jul 22 00:00:00 EDT 2025 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.5c03137· OSTI ID:2998275

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University of North Carolina, Chapel Hill, NC (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Yale University, New Haven, CT (United States)

Metal formyl complexes are critical intermediates in the reduction of CO to valuable products such as methanol and higher alcohols/hydrocarbons, yet examples of formyl generation via the catalytic hydrogenation of transition metal carbonyl complexes under mild conditions are lacking. The catalytic hydrogenation of a ruthenium carbonyl complex with H₂ to produce a formyl complex is reported here. Two classes of hydrogenation catalysts were compared: bis(diphosphine)-ligated complexes that proceed via termolecular H₂ splitting with an external base and pincer-ligated complexes that proceed via an H₂ splitting mechanism involving metal–ligand cooperativity. The hydride transfer and H₂ splitting steps were evaluated for both classes of catalysts, revealing advantages for catalysts that utilize metal–ligand cooperativity and elucidating conditions to promote formyl generation. Only the pincer-ligated Ir and Ru complexes capable of reacting via pathways involving metal–ligand cooperativity were suitable for catalysis. Using 1–10 mol % of the catalysts (PNP)Ir(H)₂ and (HPNP)Ru(H)₂(CO) (PNP = (ⁱPr₂PC₂H₄)₂N^–), which use metal–ligand cooperation to activate H₂, up to 10 turnovers or up to 71% yield were achieved for the conversion of [Ru(bpy)₂(CO)₂]²⁺ (bpy = 2,2′-bipyridine) to the formyl complex [Ru(bpy)₂(CO)(CHO)]⁺. The Lewis acid B(C₆F₅)₃ was required as an additive to achieve high yields of the formyl complex using (HPNP)Ru(H)₂(CO) as a catalyst. In conclusion, the catalytic route avoids the use of expensive stoichiometric reagents, such as borohydride, instead generating metal formyls that are key intermediates in CO reduction schemes with H₂ gas.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704; SC0021173

OSTI ID:: 2998275

Report Number(s):: BNL--229033-2025-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 15 Vol. 15; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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