biostudies-literatureBruch QJHonjo International Scholarship FoundationNational Institute of General Medical SciencesNIGMS NIH HHS21443-21447https://www.ebi.ac.uk/biostudies/studies/S-EPMC9712262biostudies-literatureUnknown144(47)Hydride transfer catalysis is shown to be enabled by the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand. Complex <b>1</b>·[Ru]⁺, comprising a nontrigonal phosphorus chelate (<b>1</b>, P(N(<i>o</i>-N(2-pyridyl)C₆H₄)₂) and an inert metal fragment ([Ru] = (Me₅C₅)Ru), reacts with NaBH₄ to give a metallohydridophosphorane (<b>1</b>^<b>H</b>·[Ru]) by P-H bond formation. Complex <b>1</b>^<b>H</b>·[Ru] is revealed to be a potent hydride donor (Δ<i>G</i>°_H-,exp < 41 kcal/mol, Δ<i>G</i>°_H-,calc = 38 ± 2 kcal/mol in MeCN). Taken together, the reactivity of the <b>1</b>·[Ru]⁺/<b>1</b>^<b>H</b>·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer.Journal of the American Chemical SocietyMetal-Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal.PMC9712262F32 GM143865R21 GM134240Tanushi ABruch QJMuller PRadosevich ATfalseMetal-Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal.Hydride transfer catalysis is shown to be enabled by the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand. Complex <b>1</b>·[Ru]⁺, comprising a nontrigonal phosphorus chelate (<b>1</b>, P(N(<i>o</i>-N(2-pyridyl)C₆H₄)₂) and an inert metal fragment ([Ru] = (Me₅C₅)Ru), reacts with NaBH₄ to give a metallohydridophosphorane (<b>1</b>^<b>H</b>·[Ru]) by P-H bond formation. Complex <b>1</b>^<b>H</b>·[Ru] is revealed to be a potent hydride donor (Δ<i>G</i>°_H-,exp < 41 kcal/mol, Δ<i>G</i>°_H-,calc = 38 ± 2 kcal/mol in MeCN). Taken together, the reactivity of the <b>1</b>·[Ru]⁺/<b>1</b>^<b>H</b>·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer.2022-01-01T00:00:00Z2022 Nov2025-04-05T10:23:26.592Z2025-02-19T04:43:58.03ZS-EPMC97122623637862610.1021/jacs.2c10200