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Updated: Aug 21, 2025

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Metal-Ligand Role Reversal: Hydride-Transfer Catalysis by a Functional Phosphorus Ligand with a Spectator Metal
Quinton J Bruch1, Akira Tanushi1, Peter Müller1
1Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Abstract:
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 (1·[Ru]) by P-H bond formation. Complex 1·[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]+/1·[Ru] pair comprises a catalytic couple, enabling catalytic hydrodechlorination in which phosphorus is the sole reactive site of hydride transfer.
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