Metal–Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal

• DOI: 10.1021/jacs.2c10200
• Publication Date: 2022-11-15T18:30:38Z
• Authors: Quinton J. Bruch; Akira Tanushi; Peter Müller; Alexander T. Rado...
• Keywords: Metals; Transition Elements; Phosphorus; Ligands; 01 natural sciences; Catalysis; 0104 chemical sciences

Hydride transfer catalysis is shown to be enabled by the nonspectator reactivity of a transition metal-bound low-symmetry tricoordinate phosphorus ligand. Complex 1·[Ru]+, comprising a nontrigonal phosphorus chelate (1, P(N(o-N(2-pyridyl)C6H4)2) and an inert metal fragment ([Ru] = (Me5C5)Ru), reacts with NaBH4 to give a metallohydridophosphorane (1H·[Ru]) by P-H bond formation. Complex 1H·[Ru] is revealed to be a potent hydride donor (ΔG°H-,exp < 41 kcal/mol, ΔG°H-,calc = 38 ± 2 kcal/mol in MeCN). Taken together, the reactivity of the 1·[Ru]+/1H·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer.