A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia.
The synthesis of transition metal-dinitrogen complexes and the stoichiometric transformation of their coordinated dinitrogen into ammonia and hydrazine have been the subject of considerable research, with a view to achieving nitrogen fixation under ambient conditions. Since a single example in 2003, no examples have been reported of the catalytic conversion of dinitrogen into ammonia under ambient conditions. The dimolybdenum-dinitrogen complex bearing PNP pincer ligands was found to work as an effective catalyst for the formation of ammonia from dinitrogen, with 23 equiv. of ammonia being produced with the catalyst (12 equiv. of ammonia are produced based on the molybdenum atom of the catalyst). This is another successful example of the catalytic and direct conversion of dinitrogen into ammonia under ambient reaction conditions. We believe that the results described in this Article provide valuable information with which to develop a more effective nitrogen-fixation system under mild reaction conditions.
Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan.
Kazuya
K
Arashiba
Yoshihiro
Y
Miyake
Yoshiaki
Y
Nishibayashi
D000641:Ammonia / Q000737:chemistry*; D002384:Catalysis; D006834:Hydrazines / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*
D006834:Hydrazines; D008024:Ligands; D011725:Pyridines; C029424:hydrazine; D000641:Ammonia; D008982:Molybdenum; D009584:Nitrogen
Angew Chem Int Ed Engl. 2006 Sep 25;45(38):6264-88
16983726
Inorg Chem. 2000 Dec 25;39(26):5946-57
11151496
J Am Chem Soc. 2007 Mar 14;129(10):2998-3006
17309262
Angew Chem Int Ed Engl. 2005 Dec 23;45(2):196-9
16342309
Acc Chem Res. 2005 Mar;38(3):208-14
15766240
Nature. 2004 Mar 18;428(6980):279-80
15029186
Dalton Trans. 2007 Jan 7;(1):16-25
17160169
Angew Chem Int Ed Engl. 2009;48(47):8832-46
19834922
Angew Chem Int Ed Engl. 2008;47(30):5512-22
18537212
Angew Chem Int Ed Engl. 2002 Jan 4;41(1):27-47
12491443
Chem Rev. 2004 Feb;104(2):385-401
14871129
Angew Chem Int Ed Engl. 2004 Oct 11;43(40):5298-308
15376300
Acc Chem Res. 2009 Jan 20;42(1):127-33
18803409
Chem Asian J. 2007 Aug 3;2(8):936-46
17614310
Chem Commun (Camb). 2010 Feb 21;46(7):1013-25
20126700
Science. 2003 Jul 4;301(5629):76-8
12843387
J Am Chem Soc. 2004 May 19;126(19):6150-63
15137780
Science. 2002 Sep 6;297(5587):1696-700
12215645
Acc Chem Res. 2005 Dec;38(12):955-62
16359167
Inorg Chem. 2001 Jan 29;40(3):578-80
11209623
Science. 1998 Jan 23;279(5350):540-2
9438842