Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex

Máté J. Bezdek, Sheng Guo, Paul J. Chirik

Science · 2016 · 242 citations · 57 references

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TL;DR

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.

Abstract

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

References

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