Catalytic reduction of dinitrogen to ammonia at a single molybdenum center

被引:1172
作者
Yandulov, DV [1 ]
Schrock, RR [1 ]
机构
[1] MIT, Dept Chem, Cambridge, MA 02139 USA
关键词
D O I
10.1126/science.1085326
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Dinitrogen (N-2) was reduced to ammonia at room temperature and 1 atmosphere with molybdenum catalysts that contain tetradentate [HIPTN3N](3-) triamidoamine ligands {such as [HIPTN3N]Mo(N-2), where [HIPTN3N](3-) is[{3,5-(2,4,6-i-Pr3C6H2)(2)C6H3NCH2CH2}(3)N](3-)} in heptane. Slow addition of the proton source [{2,6-lutidinium}{BAr'(4)}, where Ar' is 3,5-(CF3)(2)C6H3] and reductant (decamethyl chromocene) was critical for achieving high efficiency (similar to66% 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 N-2 was reduced at a sterically protected, single molybdenum center that cycled from Mo(III) through Mo(VI) states.
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页码:76 / 78
页数:3
相关论文
共 39 条
[1]   NITROGENOPENTAMMINERUTHENIUM(2) COMPLEXES [J].
ALLEN, AD ;
SENOFF, CV .
CHEMICAL COMMUNICATIONS, 1965, (24) :621-&
[2]   Modeling of the molybdenum center in the nitrogenase FeMo-cofactor [J].
Barrière, F .
COORDINATION CHEMISTRY REVIEWS, 2003, 236 (1-2) :71-89
[3]   NITROGEN-FIXATION IN SOLUTION [J].
BAZHENOVA, TA ;
SHILOV, AE .
COORDINATION CHEMISTRY REVIEWS, 1995, 144 :69-145
[4]   THE UNUSUAL METAL-CLUSTERS OF NITROGENASE - STRUCTURAL FEATURES REVEALED BY X-RAY ANOMALOUS DIFFRACTION STUDIES OF THE MOFE PROTEIN FROM CLOSTRIDIUM-PASTEURIANUM [J].
BOLIN, JT ;
RONCO, AE ;
MORGAN, TV ;
MORTENSON, LE ;
XUONG, NH .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1993, 90 (03) :1078-1082
[5]   Mechanism of molybdenum nitrogenase [J].
Burgess, BK ;
Lowe, DJ .
CHEMICAL REVIEWS, 1996, 96 (07) :2983-3011
[6]   THE IRON MOLYBDENUM COFACTOR OF NITROGENASE [J].
BURGESS, BK .
CHEMICAL REVIEWS, 1990, 90 (08) :1377-1406
[7]  
CHANEY AL, 1962, CLIN CHEM, V8, P130
[8]   RECENT ADVANCES IN CHEMISTRY OF NITROGEN-FIXATION [J].
CHATT, J ;
DILWORTH, JR ;
RICHARDS, RL .
CHEMICAL REVIEWS, 1978, 78 (06) :589-625
[9]  
CHEN J, 1993, ANGEW CHEM INT EDIT, V32, P1592
[10]   Chemical redox agents for organometallic chemistry [J].
Connelly, NG ;
Geiger, WE .
CHEMICAL REVIEWS, 1996, 96 (02) :877-910