3 years ago

Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand

Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand
Grant W. Margulieux, Máté J. Bezdek, Zoë R. Turner, Paul J. Chirik
Treatment of the bis(imino)pyridine molybdenum η6-benzene complex (iPrPDI)Mo(η6-C6H6) (iPrPDI, 2,6-(2,6-iPr2C6H3N═CMe)2C5H3N) with NH3 resulted in coordination induced haptotropic rearrangement of the arene to form (iPrPDI)Mo(NH3)22-C6H6). Analogous η2-ethylene and η2-cyclohexene complexes were also synthesized, and the latter was crystallographically characterized. All three compounds undergo loss of the η2-coordinated ligand followed by N–H bond activation, bis(imino)pyridine modification, and H2 loss. A dual ammonia activation approach has been discovered whereby reversible M–L cooperativity and coordination induced bond weakening likely contribute to dihydrogen formation. Significantly, the weakened N–H bonds in (iPrPDI)Mo(NH3)22-C2H4) enabled hydrogen atom abstraction and synthesis of a terminal nitride from coordinated ammonia, a key step in NH3 oxidation.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b03070

DOI: 10.1021/jacs.7b03070

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