Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia.
It is vital to design effective nitrogen fixation systems that operate under mild conditions, and to this end we recently reported an example of the catalytic formation of ammonia using a dinitrogen-bridged dimolybdenum complex bearing a pincer ligand, where up to twenty three equivalents of ammonia were produced based on the catalyst. Here we study the origin of the catalytic behaviour of the dinitrogen-bridged dimolybdenum complex bearing the pincer ligand with density functional theory calculations, based on stoichiometric and catalytic formation of ammonia from molecular dinitrogen under ambient conditions. Comparison of di- and mono-molybdenum systems shows that the dinitrogen-bridged dimolybdenum core structure plays a critical role in the protonation of the coordinated molecular dinitrogen in the catalytic cycle.
1] Institute for Materials Chemistry and Engineering and International Research Center for Molecular Systems, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan [2] Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Nishikyo-ku, Kyoto 615-8520, Japan [3].
Hiromasa
H
Tanaka
1] Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan [2].
Kazuya
K
Arashiba
Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan.
Shogo
S
Kuriyama
1] Institute for Materials Chemistry and Engineering and International Research Center for Molecular Systems, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan [2] Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Nishikyo-ku, Kyoto 615-8520, Japan.
Akira
A
Sasada
Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan.
Kazunari
K
Nakajima
1] Institute for Materials Chemistry and Engineering and International Research Center for Molecular Systems, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan [2] Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Nishikyo-ku, Kyoto 615-8520, Japan.
Kazunari
K
Yoshizawa
Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan.
Yoshiaki
Y
Nishibayashi
D000641:Ammonia / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D005308:Fertilizers; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009586:Nitrogen Fixation; D009942:Organometallic Compounds / Q000737:chemistry*
D005308:Fertilizers; D009942:Organometallic Compounds; D000641:Ammonia; D008982:Molybdenum