Science · 2016 · 242 citations · 57 references
Natural SciencesChemistryCrystal StructureInorganic ChemistryPhysical ChemistryChemical BondingCoordination ChemistryHydrogen AtomIntermolecular InteractionsMolecular BondingMolecular InteractionsProton Exchange Reactions
Ammonia and water are well known for proton‑exchange chemistry, whereas radical H‑atom exchange is uncommon without high‑energy stimuli. The authors employ theoretical and electrochemical analyses to explain how coordination to a molybdenum complex weakens N–H and O–H bonds. Coordination of ammonia or water to the molybdenum complex weakens their N–H or O–H bonds sufficiently that heating to 60 °C releases hydrogen. See Bezdek et al., Science, this issue p.
Coordinated scission of N–H or O–H bonds Ammonia and water both have well-explored acid-base chemistry at room temperature, revolving around proton exchange. In contrast, radical chemistry involving H-atom exchange is comparatively rare in these molecules in the absence of a high-energy stimulus. Bezdek et al. now show that coordination of ammonia or water to a molybdenum complex substantially weakens the N–H or O–H bonds, so much so that heating to 60°C liberates hydrogen (see the Perspective by Hoover). Theoretical and electrochemical analyses reveal the underpinnings of the bond-weakening phenomenon. Science , this issue p. 730 ; see also p. 707
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Density-functional thermochemistry. III. The role of exact exchange
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