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Dalton Transactions
Page 4 of 6
DOI: 10.1039/C7DT03703A
COMMUNICATION
turnover numbers and low efficiency. The complex
Journal Name
2
doesn’t CE29-0018-01). AGM is grateful to French Embassy in Moscow
suffer from this and can be used in low concentration to for the Mechnikov Fellowship. LC is indebted to Ministère de
provide turnover number up to 1000. The insertion of l’Education Nationale, de l’Enseignement Supérieur et de la
carbenes into N-H bond occurs cleaner than cyclopropanation. Recherche, France for the PhD fellowship.
Practically no EDA dimerization products were formed. The
reaction mediated by
2 was the most efficient at 90°C. In the
Notes and references
absence of the catalyst the conversion of aniline was limited to
5%. The reaction is tolerant of both electron-donating and
electron-withdrawing groups on the aromatic moiety.
Substituted anilines converted to mono- and di-insertion
1
(a) D. Intrieri, A. Caselli, F. Ragaini, P. Macchi, N. Casati and E.
Gallo, Eur. J. Inorg. Chem., 2012, 2012, 569–580; (b) P. Fackler,
S. M. Huber and T. Bach, J. Am. Chem. Soc., 2012, 134, 12869–
12878; (c) K.-H. Chan, X. Guan, V. K.-Y. Lo and C.-M. Che,
Angew. Chem. Int. Ed., 2014, 53, 2982–2987.
products with ~ 80:20 ratios. However,
2 is slightly less
efficient in the reaction with aliphatic amines (entries N and O)
providing a 58 % yield of double insertion product with 2-
methoxyethylamine and a 90 % yield with morpholine.
Previously, dinuclear Ru(I) and Ru(II) complexes with
2
3
(a) Z. Gross and S. Ini, Inorg. Chem., 1999, 38, 1446–1449; (b) C.-
J. Liu, W.-Y. Yu, C.-M. Che and C.-H. Yeung, J. Org. Chem., 1999,
64, 7365–7374; (c) C. Wang, K. V. Shalyaev, M. Bonchio, T.
Carofiglio and J. T. Groves, Inorg. Chem., 2006, 45, 4769–4782.
D. Intrieri, D. M. Carminati and E. Gallo, in Handbook of
Porphyrin Science, eds. K. M. Kadish, K. M. Smith and R. Guilard,
World Scientific, Singapore, 2016, pp. 1–99.
carboxylate,
hydrido,
silyl,
phosphane,
arene,
cyclopendadienyl and multidentate nitrogen ligands have been
used as catalysts for carbene transfer reactions.28 To the best
of our knowledge, carbene transfer reactions catalyzed by Ru
in high oxidation state are rare. Simonneaux and coworkers
have used Ru(VI) dioxo porphyrin complexes for
cyclopropanation of styrenes, but active ruthenium carbene
species was formed after reduction of Ru(VI) to Ru(II)
complexes with EDA.29 Similarly, Gross and co-workers
proposed that µ-oxo diiron(IV) and mononuclear Fe(IV) corrole
complexes should be initially reduced to Fe(III) state to react
with EDA.30 In the present case, Ru(IV)=C=Ru(IV)
phthalocyaninate appears to keep a high oxidation state. For
this reason, the activation of EDA occurs only at elevated
temperatures. Our attempts to detect a putative active
4
5
P. Zardi, D. Intrieri, D. M. Carminati, F. Ferretti, P. Macchi and E.
Gallo, J. Porphyrins Phthalocyanines, 2016, 20, 1156–1165.
(a) I. Nicolas, P. Le Maux and G. Simonneaux, Tetrahedron Lett.,
2008, 49, 5793–5795; (b) S. Fantauzzi, A. Caselli and E. Gallo,
Dalton Trans., 2009, 5434-5443; (c) W. Xiao, J. Wei, C.-Y. Zhou
and C.-M. Che, Chem. Commun., 2013, 49, 4619-4621.
M. W. Wolf, D. A. Vargas and N. Lehnert, Inorg. Chem., 2017,
56, 5623–5635.
6
7
8
A. B. Sorokin, Chem. Rev., 2013, 113, 8152–8191.
H.-H. Liu, Y. Wang, Y.-J. Shu, X.-G. Zhou, J. Wu and S.-Y. Yan, J.
Mol. Catal. A: Chem., 2006, 246, 49–52.
carbene complex formed by 2 were unsuccessful.
9
(a) T. Rawling and A. M. McDonagh, Coord. Chem. Rev., 2007,
251, 1128–1157; (b) Y. G. Gorbunova, Y. Y. Enakieva, S. G.
Sakharov and A. Y. Tsivadze, J. Porphyrins Phthalocyanines,
2003, 7, 795–800.
In conclusion, although several types of ruthenium
complexes have emerged as suitable catalysts for carbene
transfer reactions,3,28 µ-carbido diruthenium macrocyclic
complexes have not been previously considered as catalysts.
10 (a) M. S. Rodríguez-Morgade, M. Planells, T. Torres, P. Ballester
and E. Palomares, J. Mater. Chem., 2008, 18, 176-181; (b) A. N.
Cammidge, G. Berber, I. Chambrier, P. W. Hough and M. J. Cook,
Tetrahedron, 2005, 61, 4067–4074.
The original interest in the µ-carbido complex
2 was fuelled by
the observation of the particular catalytic properties of related
µ-nitrido and µ-oxo complexes.19-25 This study represents the
first example of the catalytic application of dimeric µ-carbido
Ru(IV) phthalocyaninate exemplified by the carbene insertion
reactions into olefinic bonds and N-H bonds of amines.
Although the catalytic activity is still modest, the results
obtained suggest that µ-carbido diruthenium phthalocyanine
can be added to the family of catalytically active single-atom
bridged bimetallic macrocyclic complexes and might find
interesting applications in catalysis. Recent results from Che’s
group on the remarkable catalytic properties of Ru(II)
porphyrin complexes bearing N-heterocyclic carbene ligands in
the carbene and nitrene transfer reactions31 support the
validity of our approach. Apart from the catalytic applications,
11 Y. Y. Enakieva, Y. G. Gorbunova, A. Y. Tsivadze, C. Stern and R.
Guilard, J. Porphyrins Phthalocyanines, 2007, 11, 883–890.
12 S. Omiya, M. Tsutsui, E. F. Meyer, I. Bernal and D. L. Cullen,
Inorg. Chem., 1980, 19, 134–142.
13 A. Kienast, L. Galich, K. S. Murray, B. Moubaraki, G. Lazarev, J. D.
Cashion and H. Homborg, J. Porphyrins Phthalocyanines, 1997,
1, 141–157.
14 (a) D. O. Oluwole, A. V. Yagodin, N. C. Mkhize, K. E. Sekhosana,
A. G. Martynov, Y. G. Gorbunova, A. Y. Tsivadze and T. Nyokong,
Chem. - Eur. J., 2017, 23, 2820–2830; (b) A. G. Martynov, J.
Mack, B. P. Ngoy, T. Nyokong, Y. G. Gorbunova and A. Y.
Tsivadze, Dyes Pigm., 2017, 140, 469–479.
the reported approach to µ-carbido ruthenium(IV) complexes
might also attract attention from the viewpoint of elaboration
of novel optoelectronic materials.32
15 D. Braga, F. Grepioni, P. J. Dyson, B. F. G. Johnson, P. Frediani,
M. Bianchi and F. Piacenti, J. Chem. Soc. Dalton Trans., 1992,
2565–2571.
This work was supported by the Foundation of President of
Russian Federation for support of young scientists and leading
scientific schools (grant MK-141.2017.3), Program of RAS (I.14)
and Agence Nationale de Recherches, France (grant ANR-16-
16 C. Li, J. Xu, J. Zhao, D. Tian and R. B. King, Dalton Trans., 2010,
39, 10697-10701.
17 (a) L. Ma, G. K. Williams and J. R. Shapley, Coord. Chem. Rev.,
1993, 128, 261–284; (b) S. Takemoto and H. Matsuzaka, Coord.
4 | J. Name., 2012, 00, 1-3
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