Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo-NH3Complex.
We report ammonia oxidation by homolytic cleavage of all three H atoms from a [Mo-NH3]+complex using the 2,4,6-tri-tert-butylphenoxyl radical to yield a Mo-alkylimido ([Mo═NR]+) complex (R = 2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one). Chemical reduction of [Mo═NR]+generates a terminal Mo≡N nitride complex upon N-C bond cleavage, and a [Mo═NH]+complex is formed by protonation of the nitride. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from [Mo-NH3]+and formation of [Mo═NR]+.
Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
Papri
P
Bhattacharya
Department of Chemistry, Washington State University , Pullman, Washington 99164, United States.
Zachariah M
0000-0002-7192-4441
ZM
Heiden
Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
Eric S
0000-0002-7202-9676
ES
Wiedner
Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
Simone
S
Raugei
Department of Chemistry, Villanova University , Villanova, Pennsylvania 19085, United States.
Nicholas A
NA
Piro
Department of Chemistry, Villanova University , Villanova, Pennsylvania 19085, United States.
W Scott
WS
Kassel
Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
R Morris
0000-0001-6306-4851
RM
Bullock
Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory , P.O. Box 999, Richland, Washington 99352, United States.
Michael T
0000-0002-7310-2791
MT
Mock