Unique behaviour of dinitrogen-bridged dimolybdenum complexes bearing pincer ligand towards catalytic formation of ammonia
Open Access
- 28 April 2014
- journal article
- Published by Springer Nature in Nature Communications
- Vol. 5 (1) , 3737
Abstract
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.Keywords
This publication has 67 references indexed in Scilit:
- Catalytic conversion of nitrogen to ammonia by an iron model complexNature, 2013
- Design and Preparation of Molybdenum–Dinitrogen Complexes with Ferrocenyldiphosphine and Pentamethylcyclopentadienyl Moieties as Auxiliary LigandsChemistry – A European Journal, 2013
- Testing the Polynuclear Hypothesis: Multielectron Reduction of Small Molecules by Triiron Reaction SitesJournal of the American Chemical Society, 2013
- Synthesis and Protonation of Molybdenum– and Tungsten–Dinitrogen Complexes Bearing PNP-Type Pincer LigandsOrganometallics, 2012
- N 2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium ComplexScience, 2011
- An electrochemical investigation of intermediates and processes involved in the catalyticreduction of dinitrogen by [HIPTN3N]Mo (HIPTN3N = (3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2)3N)Dalton Transactions, 2011
- Protonation of the Dinitrogen-Reduction Catalyst [HIPTN3N]MoIIIInvestigated by ENDOR SpectroscopyInorganic Chemistry, 2010
- Catalytic reduction of dinitrogen to ammonia at a single molybdenum centerProceedings of the National Academy of Sciences, 2006
- Reduction of dinitrogenProceedings of the National Academy of Sciences, 2006
- The Yandulov/Schrock Cycle and the Nitrogenase Reaction: Pathways of Nitrogen Fixation Studied by Density Functional TheoryAngewandte Chemie International Edition, 2005