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Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center
Dmitry V. Yandulov and
Richard R. Schrock*
Dinitrogen (N2) was reduced to ammonia at room temperature and1 atmosphere with molybdenum catalysts that contain tetradentate[HIPTN3N]3– triamidoamine ligands {such as [HIPTN3N]Mo(N2),where [HIPTN3N]3– is [{3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2}3N]3–}in heptane. Slow addition of the proton source [{2,6-lutidinium}{BAr'4},where Ar' is 3,5-(CF3)2C6H3]and reductant (decamethyl chromocene)was critical for achieving high efficiency (66% in four turnovers).Numerous x-ray studies, along with isolation and characterizationof six proposed intermediates in the catalytic reaction undernoncatalytic conditions, suggest that N2 was reduced at a stericallyprotected, single molybdenum center that cycled from Mo(III)through Mo(VI) states.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
* To whom correspondence should be addressed. E-mail: rrs{at}mit.edu
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