PleasDeadltoonnoTtraandsjaucsttiomnasrgins
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DOI: 10.1039/C8DT02739K
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[H(OEt2)2][BArF ] as a proton source (76 equiv) were used
2
For selected recent reviews, see: (a) K. C. MacLeod and P. L.
Holland, Nat. Chem., 2013, , 559; (b) M. D. Fryzuk, Chem.
4
5
under the same reaction conditions, 1.3 equiv of ammonia
were produced based on the zirconium atom and no hydrazine
was produced in the reaction using 2c as a catalyst (Table 1,
Entry 4). On the other hand, a mixture of ammonia and
hydrazine (0.52 equiv and 0.45 equiv based on the zirocnium
atom, respectively) was obtained in the reaction using 2c as a
Commun., 2013, 49, 4866; (c) H. Broda, S. Hinrichsen and F.
Tuczek, Coord. Chem. Rev., 2013, 257, 587; (d) Y. Tanabe and
Y. Nishibayashi, Coord. Chem. Rev., 2013, 257, 2551; (e) H.-P.
Jia and E. A. Quadrelli, Chem. Soc. Rev., 2014, 43, 547; (f) C. J.
M. van der Ham, M. T. M. Koper and D. G. H. Hetterscheid,
Chem. Soc. Rev., 2014, 43, 5183; (g) C. Köthe and C. Limberg,
Z. Anorg. Allg. Chem., 2015, 641, 18; (h) N. Khoenkhoen, B.
de Bruin, J. N. H. Reek and W. I. Dzik, Eur. J. Inorg. Chem.,
2015, 567.
catalyst when 36 equiv of CoCp*2 (Cp*
= 1,2,3,4,5-
pentamethylcyclopentadienyl) as a reductant and 48 equiv of
[Ph2NH2]OTf (OTf = OSO2CF3) as a proton source (Table 1, Entry
5). For comparsion, 2a was found to work as a less effective
catalyst than 2c, where only 0.31 equiv of ammonia were
produced together with 5.9 equiv of hydrogen gas (Table 1,
3
For selected recent examples see: (a) C. Gradert, N. Stucke, J.
Krahmer, C. Näther and F. Tuczek, Chem.-Eur. J., 2015, 21
,
1130; (b) Y. Lee, F. T. Sloane, G. Blondin, K. A. Abboud, R.
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Zavalij and L. R. Sita, Angew. Chem., Int. Ed., 2015, 54, 10220;
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Schneider, Angew. Chem., Int. Ed., 2016, 55, 4786; (e) M. M.
Entry 6).
complex 2c produced slightly larger amounts of ammonia and
hydrazine than the dinitrogen-bridged dititanium complex 1c
The use of the dinitrogen-bridged dizirconium
Guru, T. Shima and Z. Hou, Angew. Chem., Int. Ed., 2016, 55
12316; (f) F. S. Schendzielorz, M. Finger, C. Volkmann, C.
Würtele and S. Schneider, Angew. Chem., Int. Ed., 2016, 55
11417; (g) B. Wang, G. Luo, M. Nishiura, S. Hu, T. Shima, Y.
Luo and Z. Hou, J. Am. Chem. Soc. 2017, 139, 1818; (h) G. A.
Silantyev, M. Förster, B. Schluscha J. Abbenseth, C.
Würtele, C. Volkmann, M. C. Holthausen and S. Schneider,
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Ishida and H. Kawaguchi, Angew. Chem., Int. Ed., 2017, 56
9193.
,
.
,
However, these results indicate that both dinitrogen-bridged
dititanium and dizirconium complexes bearing anionic pyrrole-
based PNP-type pincer and Cp ligands did not work as catalysts
toward dinitrogen reduction under mild reaction conditions
although stoichiometric amounts of ammonia and hydrazine
were produced based on the complexes in both cases. At
present, we consider that mononuclear titanium– and
zirconium–dinitrogen complexes, which are generated in situ
from the corresponding dinitrogen-bridged dinuclear
complexes, work as active species toward the stoichiometric
transformation. A similar catalytic transformation has quite
recently been observed in the dinitrogen-bridged divanadium
complexes by our research group.14
β
,
,
4
5
6
(a) D. V. Yandulov and R. R. Schrock, Science, 2003, 301, 76;
(b) V. Ritleng, D. V. Yandulov, W. W. Weare, R. R. Schrock, A.
S. Hock and W. M. Davis, J. Am. Chem. Soc., 2004, 126, 6150;
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,
1103; (d) L. A. Wickramasinghe, T. Ogawa, R. R. Schrock and
P. Müller, J. Am. Chem. Soc., 2017, 139, 9132.
For selected recent reviews, see: (a) Y. Tanabe and Y.
Nishibayashi, Chem. Rec. 2016, 16, 1549; (b) R. J. Burford and
M. D. Fryzuk, Nat. Rev. Chem. 2017, 1, 0026; (c) Nitrogen
Fixation: Topics in Organometallic Chemistry 60, Ed: Y.
Nishibayashi, Springer, 2017; (d) Y. Roux, C. Duboc and M.
Gennari, ChemPhysChem, 2017, 18, 2606.
(a) K. Arashiba, Y. Miyake and Y. Nishibayashi, Nat. Chem.,
2011, 3, 120; (b) K. Arashiba, E. Kinoshita, S. Kuriyama, A.
Eizawa, K. Nakajima, H. Tanaka, K. Yoshizawa and Y.
Nishibayashi, J. Am. Chem. Soc., 2015, 137, 5666; (c) A.
Eizawa, K. Arashiba, H. Tanaka, S. Kuriyama, Y. Matsuo, K.
Nakajima, K. Yoshizawa and Y. Nishibayashi, Nat. Commun.
In summary, we have newly designed and prepared some
titanium and zirconium complexes bearing a pyrrole-based
PNP-type pincer ligand. Dinitrogen-bridged dititanium and
dizirconium complexes bearing both pincer and Cp ligands
have been prepared and characterized by X-ray analysis. The
nature of the bridging dinitrogen ligand has been characterized
by DFT calculations. Unfortunately, both dinitrogen-bridged
dititanium and dizirconium complexes produced only
stoichiometric amounts of ammonia and hydrazine under mild
reaction conditions, however, we believe the present result
described in this paper provides useful information to develop
more effective titanium– and zirconium–dinitrogen complexes
toward catalytic nitrogen fixation in near future. Further
study is currently in progress.
2017,
K. Arashiba , A. Eizawa, H. Tanaka, K. Nakajima, K. Yoshizawa
and Y. Nishibayashi, Bull. Chem. Soc. Jpn., 2017, 90, 1111.
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7
8
,
84; (b) T. M. Buscagan, P. H. Oyala and J. C. Peters, Angew.
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S. Kuriyama, K. Arashiba, K. Nakajima, Y. Matsuo, H. Tanaka,
K. Ishii, K. Yoshizawa and Y. Nishibayashi, Nat. Commun.,
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9
10 P. J. Hill, L. R. Doyle, A. D. Crawford, W. K. Myers and A. E.
Ashley, J. Am. Chem. Soc., 2016, 138, 13521.
11 T. J. D. Castillo, N. B. Thompson, D. L. M. Suess, G. Ung, and J.
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12 S. Kuriyama, K. Arashiba, H. Tanaka, Y. Matsuo, K. Nakajima,
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13 J. Fajardo and J. C. Peters, J. Am. Chem. Soc., 2017, 139
16105.
The present project is supported by CREST, JST
(JPMJCR1541). We thank Grants-in-Aid for Scientific Research
(Nos. JP17H01201 and JP15H05798) from JSPS and MEXT. A.E.
is a recipient of the JSPS Predoctoral Fellowships for Young
Scientists.
,
14 Y. Sekiguchi, K. Arashiba, H. Tanaka, A. Eizawa, K. Nakajima,
K. Yoshizawa and Y. Nishibayashi, Angew. Chem., Int. Ed.,
2018, 57, 9064.
Notes and references
15 L. R. Doyle, A. J. Wooles, L. C. Jenkins, F. Tuna, E. J. L.
‡ Previously Vol’pin group and Shilov group tried to develop
catalytic reduction of molecular dinitrogen using titanium
complexes under ambient reaction conditions; however, only up
to a stoichiometric amount of ammonia was produced based on
the titanium atom of the catalyst.16
McInnes and S. T. Liddle, Angew. Chem., Int. Ed., 2018, 57
6314.
,
16 (a) M. E. Vol’pin, J. Organomet. Chem., 1980, 200, 319; (b) A.
E. Shilov, Russ. Chem. Bull., 2003, 52, 2555.
17 A. W. Addison, T. N. Rao, J. Reedijk, J. van Rijn and G. C.
Verschoor, J. Chem. Soc. Dalton Trans., 1984, 1349.
1
Ammonia synthesis catalysts: Innovation and Practice, Ed: H.
Liu, World Scientific, Beijing, 2013.
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