Catalytic reduction of dinitrogen with protons and electrons continues to demand new approaches.  As a consequence of Nishibayashi's report of catalytic reduction of dinitrogen employing a neutral molybdenum complex that contains a neutral PNP-type pincer ligand, we have turned to the synthesis of monoanionic pincer complexes of molybdenum.  We have synthesized (t-BuPOCOP)MoI2 (1 ; t-BuPOCOP = C6H3-1,3-[OP(t-Bu)2]2) from MoI3(THF)3.  Reduction of 1  under dinitrogen facilitates the six electron cleavage of N2 to form a terminal nitrido complex, [(t-BuPOCOP)Mo(I)(N)]- (2) .  The origin of the N atom was confirmed using 15N2.  Protonation of [(t-BuPOCOP)Mo(I)(N)]- results in formation of an unusual neutral species in which the proton has added across the Mo-P bond, not at the terminal nitride.  Initial studies reveal that 2  is not a catalyst for the reduction of dinitrogen to ammonia under conditions that we have employed in the past or those employed by Nishibayashi.

Cleavage of dinitrogen by a molybdenum pincer complex to give a molybdenum nitride

243rd National Meeting (2012)

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