Page 5 of 7
Journal of the American Chemical Society
1
2
3
4
Dinitrogen-bridged Dimolybdenum Complexes Bearing Pincer Ligand
towards Catalytic Formation of Ammonia. Nat. Commun. 2014, 5, 3737-
Nishibayashi, Y. Synthesis and Reactivity of Iron– and Cobalt–Dinitrogen
Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation.
Eur. J. Inorg. Chem. 2017, 3769-3778. (d) Siedschlag, R. B.; Bernales, V.;
Vogiatzis, K. D.; Planas, N.; Clouston, L. J.; Bill, E.; Gagliardi, L.; Lu, C.
C. Catalytic Silylation of Dinitrogen with a Dicobalt Complex. J. Am. Chem.
Soc. 2015, 137, 4638-4641. (e) Imayoshi, R.; Tanaka, H.; Matsuo, Y.; Yuki,
M.; Nakajima, K.; Yoshizawa, K.; Nishibayashi, Y. Cobalt-Catalyzed
Transformation of Molecular Dinitrogen into Silylamine under Ambient
Reaction Conditions. Chem. Eur. J. 2015, 21, 8905-8909.
3
747. (f) Kinoshita, E.; Arashiba, K.; Kuriyama, S.; Miyake, Y.; Shimazaki,
R.; Nakanishi, H.; Nishibayashi, Y. Synthesis and Catalytic Activity of
Molybdenum–Dinitrogen Complexes Bearing Unsymmetric PNP-Type
Pincer Ligands. Organometallics 2012, 31, 8437-8443. (g) Arashiba, K.;
Miyake, Y.; Nishibayashi, Y. A Molybdenum Complex Bearing PNP-type
Pincer Ligands Leads to the Catalytic Reduction of Dinitrogen into
Ammonia. Nat. Chem. 2011, 3, 120-125. (h) Schrock, R. R. Catalytic
Reduction of Dinitrogen to Ammonia by Molybdenum: Theory versus
Experiment. Angew. Chem., Int. Ed. 2008, 47, 5512-5522. (i) Weare, W.
W.; Dai, X.; Byrnes, M. J.; Chin, J. M.; Schrock, R. R. Catalytic Reduction
of Dinitrogen to Ammonia at a Single Molybdenum Center. Proc. Natl.
Acad. Sci. 2006, 103, 17099-17106. (j) Schrock, R. R. Catalytic Reduction
of Dinitrogen to Ammonia at a Single Molybdenum Center. Acc. Chem. Res.
2005, 38, 955-962. (k) Ritleng, V.; Yandulov, D. V.; Weare, W. W.;
Schrock, R. R.; Hock, A. S.; Davis, W. M. Molybdenum Triamidoamine
Complexes that Contain Hexa-tert-butylterphenyl, Hexamethylterphenyl,
or p-Bromohexaisopropylterphenyl Substituents. An Examination of Some
Catalyst Variations for the Catalytic Reduction of Dinitrogen. J. Am. Chem.
Soc. 2004, 126, 6150-6163. (l) Yandulov, D. V.; Schrock, R. R. Catalytic
Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center.
Science 2003, 301, 76-78.
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5
5
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5
5
5
5
5
6
(8) Imayoshi, R.; Nakajima, K.; Nishibayashi, Y. Vanadium-Catalyzed
Reduction of Molecular Dinitrogen into Silylamine under Ambient
Reaction Conditions. Chem. Lett. 2017, 46, 466-468.
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1
2
3
4
5
6
7
8
9
0
1
2
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4
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(9) (a) Ohki, Y.; Araki, Y.; Tada, M.; Sakai, Y. Synthesis and
Characterization of Bioinspired [Mo
Their Application in the Catalytic Silylation of N
13240-13248. (b) Liao, Q.; Saffon-Merceron, N.; Mézailles, N. N
2
Fe
2
]-Hydride Cluster Complexes and
2
. Chem. Eur. J. 2017, 23,
2
Reduction into Silylamine at Tridentate Phosphine/Mo Center: Catalysis
and Mechanistic Study. ACS Catal. 2015, 5, 6902-6906. (c) Liao, Q.;
Saffon-Merceron, N.; Mézailles, N. Catalytic Dinitrogen Reduction at the
Molybdenum Center Promoted by a Bulky Tetradentate Phosphine Ligand.
Angew. Chem., Int. Ed. 2014, 53, 14206-14210. (d) Ogawa, T.; Kajita, Y.;
Wasada-Tsutsui, Y.; Wasada, H.; Masuda, H. Preparation, Characterization,
and Reactivity of Dinitrogen Molybdenum Complexes with
Bis(diphenylphosphino)amine Derivative Ligands that Form a Unique
4-Membered P-N-P Chelate Ring. Inorg. Chem. 2013, 52, 182-195. (e)
Tanaka, H.; Sasada, A.; Kouno, T.; Yuki, M.; Miyake, Y.; Nakanishi, H.;
Nishibayashi, Y.; Yoshizawa, K. Molybdenum-Catalyzed Transformation
of Molecular Dinitrogen into Silylamine: Experimental and DFT Study on
the Remarkable Role of Ferrocenyldiphosphine Ligands. J. Am. Chem. Soc.
2011, 133, 3498-3506. (f) Komori, K.; Oshita, H.; Mizobe, Y.; Hidai, M.
Preparation and Properties of Molybdenum and Tungsten Dinitrogen
Complexes. Catalytic Conversion of Molecular Nitrogen into Silylamines
Using Molybdenum and Tungsten Dinitrogen Complexes. J. Am. Chem.
Soc. 1989, 111, 1939-1940. For a Mo-based Catalytic Functionalization of
(4) (a) Sekiguchi, Y.; Arashiba, K.; Tanaka, H.; Eizawa, A.; Nakajima, K.;
Yoshizawa, K.; Nishibayashi, Y. Catalytic Reduction of Molecular
Dinitrogen to Ammonia and Hydrazine Using Vanadium Complexes.
Angew. Chem., Int. Ed. 2018, 57, 9064-9068. (b) Doyle, L. R.; Wooles, A.
J.; Jenkins, L. C.; Tuna, F.; McInnes, E. J. L.; Liddle, S. T. Catalytic
Dinitrogen Reduction to Ammonia at a Triamidoamine-Titanium Complex.
Angew. Chem., Int. Ed. 2018, 57, 6314-6318. (c) Fajardo Jr, J.; Peters, J. C.
Catalytic Nitrogen-to-Ammonia Conversion by Osmium and Ruthenium
Complexes. J. Am. Chem. Soc. 2017, 139, 16105-16108. (d) Kuriyama, S.;
Arashiba, K.; Tanaka, H.; Matsuo, Y.; Nakajima, K.; Yoshizawa, K.;
Nishibayashi, Y. Direct Transformation of Molecular Dinitrogen into
Ammonia Catalyzed by Cobalt Dinitrogen Complexes Bearing Anionic
PNP Pincer Ligands. Angew. Chem., Int. Ed. 2016, 55, 14291-14295. (e)
Castillo, T. J. D.; Thompson, N. B.; Suess, D. L. M.; Ung, G.; Peters, J. C.
N
2
to Borylamine, see: (g) Espada, M. F.; Bennaamane, S.; Liao, Q.; Saffon-
Merceron, N.; Massou, S.; Clot, E.; Nebra, N.; Fustier-Boutignon, M.;
Mézailles, N. Room-Temperature Functionalization of N to Borylamine at
2
Evaluating Molecular Cobalt Complexes for the Conversion of N
2
to NH
3
.
a Molybdenum Complex. Angew. Chem., Int. Ed. 2018, 57, 12865-12868.
(10) Kendall, A. J.; Johnson, S. I.; Bullock, R. M.; Mock, M. T. Catalytic
Inorg. Chem. 2015, 54, 9256-9262.
(5) Shiina, K. Reductive Silylation of Molecular Nitrogen via Fixation to
Tris(trialkylsilyl)amine. J. Am. Chem. Soc. 1972, 94, 9266-9267.
Silylation of N
2
and Synthesis of NH
3
and N
2 4
H by Net Hydrogen Atom
Transfer Reactions Using a Chromium P
4
Macrocycle. J. Am. Chem. Soc.
(6) (a) Piascik, A. D.; Li, R.; Wilkinson, H. J.; Green, J. C.; Ashley, A. E.
2018, 140, 2528-2536.
(11) (a) Egbert, J. D.; O’Hagan, M.; Wiedner, E. S.; Bullock, R. M.; Piro,
Fe-Catalyzed Conversion of N to N(SiMe via an Fe-Hydrazido Resting
2
3
)
3
State. J. Am. Chem. Soc. 2018, 140, 10691-10694. (b) Bai, Y.; Zhang, J.;
Cui, C. An Arene-Tethered Silylene Ligand Enabling Reversible
Dinitrogen Binding to Iron and Catalytic Silylation. Chem. Commun. 2018,
N. A.; Kasselb, W. S.; Mock, M. T. Putting Chromium on the Map for N
Reduction: Production of Hydrazine and Ammonia. A study of cis-M(N
2
2
)
2
(M = Cr, Mo, W) Bis(diphosphine) Complexes. Chem. Commun. 2016, 52,
9343-9346. (b) Akturk, E. S.; Yap, G. P. A.; Theopold, K. H. Mechanism-
Based Design of Labile Precursors for Chromium(I) Chemistry. Chem.
Commun. 2015, 51, 15402-15405. (c) Mock, M. T.; Chen, S.; O’Hagan, M.;
Rousseau, R.; Dougherty, W. G.; Kassel, W. S.; Bullock, R. M. Dinitrogen
Reduction by a Chromium(0) Complex Supported by a 16-Membered
Phosphorus Macrocycle. J. Am. Chem. Soc. 2013, 135, 11493-11496. (d)
Monillas, W. H.; Young, J. F.; Yap, G. P. A.; Theopold, K. H. A Well-
Defined Model System for the Chromium Catalyzed Selective
Oligomerization of Ethylene. Dalton Trans. 2013, 42, 9198-9210. (e) Mock,
M. T.; Chen, S.; Rousseau, R.; O’Hagan, M. J.; Dougherty, W. G.; Kassel,
W. S.; DuBois, D. L.; Bullock, R. M. A Rare Terminal Dinitrogen Complex
of Chromium. Chem. Commun. 2011, 47, 12212-12214. (f) Monillas, W.
H.; Yap, G. P. A.; Theopold, K. H. Reactivity of a Low-valent Chromium
Dinitrogen Complex. Inorg. Chim. Acta. 2011, 369, 103-119. (g) Hoffert,
W. A.; Rappe, A. K.; Shores, M. P. Unusual Electronic Effects Imparted by
Bridging Dinitrogen: an Experimental and Theoretical Investigation. Inorg.
Chem. 2010, 49, 9497-9507. (h) Berben, L. A.; Kozimor, S. A. Dinitrogen
and Acetylide Complexes of Low-Valent Chromium. Inorg. Chem. 2008,
47, 4639-4647. (i) Vidyaratne, I.; Scott, J.; Gambarotta, S.; Budzelaar, P. H.
M. Dinitrogen Activation, Partial Reduction, and Formation of Coordinated
Imide Promoted by a Chromium Diiminepyridine Complex. Inorg. Chem.
2007, 46, 7040-7049. (j) Monillas, W. H.; Yap, G. P. A.; MacAdams, L. A.;
Theopold, K. H. Binding and Activation of Small Molecules by Three-
Coordinate Cr(I). J. Am. Chem. Soc. 2007, 129, 8090-8091. (k) Zhang, Q.-
F.; Chim, J. L. C.; Lai, W.; Wong, W.-T.; Leung, W.-H. Bridged Dinitrogen
Complexes of Iron and Chromium Porphyrins. Inorg. Chem. 2001, 40,
2470-2471. (l) Denholm, S.; Hunter, G.; Weakley, T. J. R. Dinitrogen
5
4, 8124-8127. (c) Cavaillé, A.; Joyeux, B.; Saffon-Merceron, N.; Nebra,
N.; Fustier-Boutignona, M.; Mézailles, N. Triphos-Fe Dinitrogen and
Dinitrogen-Hydride Complexes: Relevance to Catalytic N Reductions.
2
Chem. Commun. 2018, 54, 11953-11956. (d) Ferreira, R. B.; Cook, B. J.;
Knight, B. J.; Catalano, V. J.; García-Serres, R.; Murray, L. J. Catalytic
Silylation of Dinitrogen by a Family of Triiron Complexes. ACS Catal.
2
018, 8, 7208-7212. (e) Fan, Y.; Chen, J.; Gao, Y.; Shi, M.; Deng, L. Iron
Dinitrogen Complexes Supported by Tris(NHC)borate Ligand: Synthesis,
Characterization, and Reactivity Study. Acta Chim. Sinica 2018, 76, 445-
452. (f) Araake, R.; Sakadani, K.; Tada, M.; Sakai, Y.; Ohki, Y. [Fe
Fe Hydride Clusters Supported by Phosphines: Synthesis,
Characterization, and Application in N Reduction. J. Am. Chem. Soc. 2017,
39, 5596-5606. (g) Prokopchuk, D. E.; Wiedner, E. S.; Walter, E. D.;
Popescu, C. V.; Piro, N. A.; Kassel, W. S.; Bullock, R. M.; Mock, M. T.
Catalytic N Reduction to Silylamines and Thermodynamics of N Binding
4
] and
[
6
]
2
1
2
2
at Square Planar Fe. J. Am. Chem. Soc. 2017, 139, 9291-9301. (h) Doyle,
L. R.; Hill, P. J.; Wildgooseb, G. G.; Ashley, A. E. Teaching Old
Compounds New Tricks: Efficient
N
2
Fixation by Simple
Fe(N )(diphosphine) Complexes. Dalton Trans. 2016, 45, 7550-7554. (i)
2
2
Yuki, M.; Tanaka, H.; Sasaki, K.; Miyake, Y.; Yoshizawa, K.; Nishibayashi,
Y. Iron-Catalysed Transformation of Molecular Dinitrogen into Silylamine
under Ambient Conditions. Nat. Commun. 2012, 3, 1254-1259.
(7) (a) Gao, Y.; Li, G.; Deng, L. Bis(dinitrogen)cobalt(−1) Complexes with
NHC Ligation: Synthesis, Characterization, and Their Dinitrogen
Functionalization Reactions Affording Side-on Bound Diazene Complexes.
J. Am. Chem. Soc. 2018, 140, 2239-2250. (b) Suzuki, T.; Fujimoto, K.;
Takemoto, Y.; Wasada-Tsutsui, Y.; Ozawa, T.; Inomata, T.; Fryzuk, M. D.;
6
Masuda, H. Efficient Catalytic Conversion of Dinitrogen to N(SiMe
Using a Homogeneous Mononuclear Cobalt Complex. ACS Catal. 2018, 8,
011-3015. (c) Imayoshi, R.; Nakajima, K.; Takaya, J.; Iwasawa, N.;
3
)
3
Complexes derived from Tricarbonyl(η -hexaethylbenzene)-chromium(0):
6
Crystal and Molecular Structure of p-Dinitrogenbis[dicarbonyl(η -
3
hexaethyl benzene)chromium(0)]-Toluene. J. Chem. Soc., Dalton Trans.
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