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

doi:10.1021/jacs.7b03070

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

Chemistry

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80 Scopus citations

Abstract

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)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.

Original language	English (US)
Pages (from-to)	6110-6113
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	17
DOIs	https://doi.org/10.1021/jacs.7b03070
State	Published - May 3 2017

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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

abstract = "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)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.",

author = "Margulieux, {Grant W.} and Bezdek, {M{\'a}t{\'e} J.} and Turner, {Zo{\"e} R.} and Chirik, {Paul J.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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doi = "10.1021/jacs.7b03070",

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T1 - Ammonia Activation, H2 Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand

AU - Margulieux, Grant W.

AU - Bezdek, Máté J.

AU - Turner, Zoë R.

AU - Chirik, Paul J.

PY - 2017/5/3

Y1 - 2017/5/3

N2 - 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)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.

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

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