Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand.
J Am Chem Soc
; 139(17): 6110-6113, 2017 05 03.
Article
em En
| MEDLINE
| ID: mdl-28414434
ABSTRACT
Treatment of the bis(imino)pyridine molybdenum η6-benzene complex (iPrPDI)Mo(η6-C6H6) (iPrPDI, 2,6-(2,6-iPr2C6H3NâCMe)2C5H3N) with NH3 resulted in coordination induced haptotropic rearrangement of the arene to form (iPrPDI)Mo(NH3)2(η2-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)2(η2-C2H4) enabled hydrogen atom abstraction and synthesis of a terminal nitride from coordinated ammonia, a key step in NH3 oxidation.
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MEDLINE
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En
Ano de publicação:
2017
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Article