Publication Date:
2003-07-05
Description:
Dinitrogen (N2) was reduced to ammonia at room temperature and 1 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 ( approximately 66% in four turnovers). Numerous x-ray studies, along with isolation and characterization of six proposed intermediates in the catalytic reaction under noncatalytic conditions, suggest that N2 was reduced at a sterically protected, single molybdenum center that cycled from Mo(III) through Mo(VI) states.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Yandulov, Dmitry V -- Schrock, Richard R -- GM 31978/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 2003 Jul 4;301(5629):76-8.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/12843387" target="_blank"〉PubMed〈/a〉
Keywords:
Ammonia/*chemistry
;
Atmospheric Pressure
;
Catalysis
;
Chromium/chemistry
;
Electrons
;
Ligands
;
Magnetic Resonance Spectroscopy
;
Molybdenum/*chemistry
;
Nitrogen/*chemistry
;
Nitrogenase/metabolism
;
Organometallic Compounds/chemistry
;
Oxidation-Reduction
;
Protons
;
Temperature
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
,
Chemistry and Pharmacology
,
Computer Science
,
Medicine
,
Natural Sciences in General
,
Physics
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