{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Bruch QJ"],"funding":["Honjo International Scholarship Foundation","National Institute of General Medical Sciences","NIGMS NIH HHS"],"pagination":["21443-21447"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9712262"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["144(47)"],"pubmed_abstract":["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]<sup>+</sup>, comprising a nontrigonal phosphorus chelate (<b>1</b>, P(N(<i>o</i>-N(2-pyridyl)C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>) and an inert metal fragment ([Ru] = (Me<sub>5</sub>C<sub>5</sub>)Ru), reacts with NaBH<sub>4</sub> to give a metallohydridophosphorane (<b>1</b><sup><b>H</b></sup>·[Ru]) by P-H bond formation. Complex <b>1</b><sup><b>H</b></sup>·[Ru] is revealed to be a potent hydride donor (Δ<i>G</i>°<sub>H-,exp</sub> < 41 kcal/mol, Δ<i>G</i>°<sub>H-,calc</sub> = 38 ± 2 kcal/mol in MeCN). Taken together, the reactivity of the <b>1</b>·[Ru]<sup>+</sup>/<b>1</b><sup><b>H</b></sup>·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer."],"journal":["Journal of the American Chemical Society"],"pubmed_title":["Metal-Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal."],"pmcid":["PMC9712262"],"funding_grant_id":["F32 GM143865","R21 GM134240"],"pubmed_authors":["Tanushi A","Bruch QJ","Muller P","Radosevich AT"],"additional_accession":[]},"is_claimable":false,"name":"Metal-Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal.","description":"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]<sup>+</sup>, comprising a nontrigonal phosphorus chelate (<b>1</b>, P(N(<i>o</i>-N(2-pyridyl)C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>) and an inert metal fragment ([Ru] = (Me<sub>5</sub>C<sub>5</sub>)Ru), reacts with NaBH<sub>4</sub> to give a metallohydridophosphorane (<b>1</b><sup><b>H</b></sup>·[Ru]) by P-H bond formation. Complex <b>1</b><sup><b>H</b></sup>·[Ru] is revealed to be a potent hydride donor (Δ<i>G</i>°<sub>H-,exp</sub> < 41 kcal/mol, Δ<i>G</i>°<sub>H-,calc</sub> = 38 ± 2 kcal/mol in MeCN). Taken together, the reactivity of the <b>1</b>·[Ru]<sup>+</sup>/<b>1</b><sup><b>H</b></sup>·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer.","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Nov","modification":"2025-04-05T10:23:26.592Z","creation":"2025-02-19T04:43:58.03Z"},"accession":"S-EPMC9712262","cross_references":{"pubmed":["36378626"],"doi":["10.1021/jacs.2c10200"]}}