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Dimension and bridging ligand effects on Mo-mediated catalytic transformation of dinitrogen to ammonia: Chain-like extended models of Nishibayashi’s catalyst

Journal Article · · Computational and Theoretical Chemistry
 [1];  [2];  [1];  [1]
  1. Sichuan Univ., Shichuan (People's Republic of China)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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Previous studies suggested that in Nishibayashi’s homogenous catalytic systems based on molybdenum (Mo) complexes, the bimetallic structure facilitated dinitrogen to ammonia conversion in comparison to the corresponding monometallic complexes, likely due to the through-bond interactions between the two Mo centers. However, more detailed model systems are necessary to support this bimetallic hypothesis, and to elucidate the multi-metallic effects on the catalytic mechanism. In this work, we computationally examined the effects of dimension as well as the types of bridging ligands on the catalytic activities of molybdenum-dinitrogen complexes by using a set of extended model systems based on Nishibayashi’s bimetallic structure. The polynuclear chains containing four ([Mo]4) or more Mo centers were found to drastically enhance the catalytic performance by comparing with both the monometallic and bimetallic complexes. Carbide ([:C≡C:]2–) was found to be a more effective bridging ligand than N2 in terms of electronic charges dispersion between metal centers thereby facilitating reactions in the catalytic cycle. Furthermore, the mechanistic modelling suggests that in principle, more efficient catalytic system for N2 to NH3 transformation might be obtained by extending the polynuclear chain to a proper size in combination with an effective bridging ligand for charge dispersion.
Research Organization:
Los Alamos National Laboratory (LANL)
Sponsoring Organization:
LDRD; USDOE
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1329598
Report Number(s):
LA-UR-16-24481
Journal Information:
Computational and Theoretical Chemistry, Journal Name: Computational and Theoretical Chemistry Journal Issue: C Vol. 1095; ISSN 2210-271X
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ammonia production
N2 to NH3
DFT
homogeneous catalysis