US EPA

3842831 

Journal Article 

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

Margulieux, GW; Bezdek, MJ; Turner, ZR; Chirik, PJ 

2017 

Yes 

Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126 

139 

17 

6110-6113 

English 

28414434 

10.1021/jacs.7b03070 

WOS:000400802300023 

https://www.proquest.com/docview/2000368250?accountid=171501&bdid=64576&_bd=2stdjnmXf2C%2FFZOqIOQdn8usNBM%3D
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Treatment of the bis(imino)pyridine molybdenum η(6)-benzene complex ((iPr)PDI)Mo(η(6)-C6H6) ((iPr)PDI, 2,6-(2,6-iPr2C6H3N═CMe)2C5H3N) with NH3 resulted in coordination induced haptotropic rearrangement of the arene to form ((iPr)PDI)Mo(NH3)2(η(2)-C6H6). Analogous η(2)-ethylene and η(2)-cyclohexene complexes were also synthesized, and the latter was crystallographically characterized. All three compounds undergo loss of the η(2)-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 ((iPr)PDI)Mo(NH3)2(η(2)-C2H4) enabled hydrogen atom abstraction and synthesis of a terminal nitride from coordinated ammonia, a key step in NH3 oxidation.