Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum

Catalysis Without Precious Metals. Edited by R. Morris Buiiock 2010 WiLEY-VCH Veriag GmbH Co. KGaA, Weinheim iSBN 978-3-527-32354-8 

NMR techniques provide valuable information for identifying and following the chemistry of paramagnetic Mo triamidoamine complexes, since nuclei that are not directly bound to the metal can often be observed and chemical shifts and line widths are not as large as with first row metal analogs. For example, the number and chemical shifts of the backbone methylene resonances in particular can be diagnostic. In a few species the backbone methylene resonances cannot be observed, for reasons that have not been elucidated. 

A significant number of theoretical calculations have been carried out on triami-doamine complexes, especially Mo complexes that are relevant to the reduction of dinitrogen. These calculations have been discussed recently and compared with experiment [57]. Perhaps the most relevant calculations are those carried out by Reiher and his group on complexes with the full [HlPTNsN] ligand set. Only calculations on complexes with the full [HlPTNsN] ligand set will be mentioned here [58-60]. 

Possible [HIPTNsNJMo Intermediates in a Catalytic Reduction of Molecular Nitrogen 

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Schrock RR. Catalytic reduction of dinitrogen to ammonia by molybdenum theory versus experiment. Angew Chent Int Ed. 2008 47 5512-5522. 

We found these conditions by introducing surface-active materials to a solution of a specially prepared catalytic complex containing molybdenum and stabilized by magnesium ions [22]. The structure of the complex which was isolated from the solution in its oxidized form is presented on Figure 5 [23]. When it is reduced to the Mo state the complex becomes an active catalyst of dinitrogen reduction to hydrazine and ammonia by sodium amalgam. Phospholipid (phosphatidylcholine)... 

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