Formic Acid Dehydrogenation Catalysis Using Novel Pyridyl‐Formamidine Half‐Sandwich Ruthenium(II) Complexes

• DOI: 10.1002/aoc.70016
• Publication Date: 2025-02-06T05:40:46Z
• Authors: Juliana Mana Edor; M. Cassiem Joseph; Johan H. L. Jordaan; Hermanus C. M. Vo...; Andrew J. Swarts
• Keywords: Reactivity; Homogeneous Catalysis; IMes

ABSTRACT The reaction of N,N′‐bidentate chelating ligands with [Ru( p ‐cymene)Cl 2 ] in methanol resulted six‐membered Ru complexes tshe general formula [RuCl( ‐cymene) L ]Cl exhibiting a pseudo‐octahedral piano‐stool geometry. combination NMR, MS, FTIR and SCXRD techniques confirmed the successful synthesis reported compounds. prepared were all active formic acid dehydrogenation (FADH) catalysis, producing an equimolar mixture H CO gases no detectable amount CO. Establishing thermodynamic kinetic parameters provided evidence for role pre‐catalyst FA during catalysis. Reactivity studies between C6 HCOOK revealed complex equilibria allowed detection key monohydride species involved Remarkably, proved to be robust at 100°C, resulting approximately 98% substrate conversion total TON about 7892 TOF close 300 h −1 after 35 h.