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Cu2+ disappeared. The resulting reaction mixture was cooled to Petersburg State University (Centres for Magnetic Resonance,
RT, the copper wire was removed and the vial was again closed for Chemical Analysis and Materials Research, and for X-ray
with the cap. The obtained white suspension in water was Diffraction Studies).
cooled in fridge to complete the precipitation of the product. It
was then centrifuged, white solid was consistently washed and
centrifuged twice with 5 ml of water (containing 0.1 g of
acetonitrile), two times with 5 ml of ethyl acetate/ethanol 1 : 1
Notes and references
mixture (containing 0.2 g of acetonitrile) and twice with 5 ml of
ethyl acetate (containing 0.1 g of acetonitrile). The obtained
precipitate was dried at 50 ꢁC in air for 2 hours and then in
vacuum at RT to give 4.34 g of the product as white crystalline
solid (yield 86%). 19F NMR (acetone-d6, 298 K; d): ꢀ151.35 (s,
BF4). 1H NMR (acetone-d6, 298 K; d): 2.22 (s, Cu–N^C–Me),
Anal. calcd for C8H12BCuF4N4: C, 30.16; H, 3.85; N, 17.81 found:
C, 30.62; H, 3.83; N, 17.78. IR (in Nujol, n) 2275 (m), 2304 (m)
1 E. J. Parish, H. Qin, B. H. Lipshutz and C. Lee, Encycl. Reagents
Org. Synth., 2007, DOI: 10.1002/9780470842898.rt039.pub2.
2 F. Wang, P. Chen and G. Liu, Encycl. Reagents Org. Synth.,
2017, DOI: 10.1002/047084289X.rn02002.
3 B. Feng, L.-Q. Lu, J.-R. Chen, G. Feng, B.-Q. He, B. Lu and
W.-J. Xiao, Angew. Chem., Int. Ed., 2018, 57, 5888–5892.
´
´
´
4 J. Garcıa-Alvarez, J. Dıez and J. Gimeno, Green Chem., 2010,
12, 2127–2130.
(C^N); 1050 (vs), 521 (s) (BF4) cmꢀ1
.
5 S. M. Soria-Castro, D. M. Andrada, D. A. Caminos,
J. E. Arguello, M. Robert and A. B. Penenory, J. Org. Chem.,
2017, 82, 11464–11473.
6 X.-H. Ouyang, C. Hu, R.-J. Song and J.-H. Li, Org. Lett., 2018,
20, 4659–4662.
7 S. Seo and M. C. Willis, Org. Lett., 2017, 19, 4556–4559.
8 J. M. Hoover, J. E. Steves and S. S. Stahl, Nat. Protoc., 2012, 7,
1161.
9 X.-Y. Yu, Q.-Q. Zhao, J. Chen, J.-R. Chen and W.-J. Xiao,
Angew. Chem., Int. Ed., 2018, 57, 15505–15509.
[Cu(CH3CN)4][PF6]. Copper(II) sulphate pentahydrate
(1.00 g, 4.0 mmol), potassium hexauorophosphate (1.99 g,
10.8 mmol, other alkali metal hexauorophosphate can be
used instead), acetonitrile (1.35 g, 32.9 mmol), distilled water
(ca. 11 ml) were used as starting reagents. The product has
been obtained as white crystalline solid, 2.60 g (yield
87%).19F NMR (acetone-d6, 298 K; d): ꢀ72.63 (d, JP–F
¼
707.4 Hz, PF6). 1H NMR (acetone-d6, 298 K; d): 2.22 (s, Cu–
N^C–Me), Anal. calcd for C8H12CuF6N4P: C, 25.78; H,
3.25; N, 15.03 Found: C, 25.61; H, 3.24; N, 15.14. IR (in Nujol, 10 H.-J. Zhang and L. Yin, J. Am. Chem. Soc., 2018, 140, 12270–
n) 2275 (m), 2311 (m) (C^N); 850 (vs), 557 (s) (PF6) cmꢀ1
12279.
[Cu(CH3CN)4][ClO4]. Copper(II) sulphate pentahydrate 11 T. C. Malig, D. Yu and J. E. Hein, J. Am. Chem. Soc., 2018, 140,
(2.00 g, 8.0 mmol), lithium perchlorate (2.30 g, 21.6 mmol,
9167–9173.
other alkali metal perchlorate can be used instead), aceto- 12 P. K. Chikkade, Y. Kuninobu and M. Kanai, Chem. Sci., 2015,
nitrile (2.68 g, 65.4 mmol), distilled water (ca. 9 ml) were used 6, 3195–3200.
as starting reagents. The product has been obtained as white 13 L. Maestre, E. Ozkal, C. Ayats, A. Beltran, M. M. Dıaz-
.
´
´
´
crystalline solid, 4.29 g of (yield 82%).1H NMR (acetone-d6,
298 K; d): 2.22 (s, Cu–N^C–Me), Anal. calcd for C8H12
Requejo, P. J. Perez and M. A. Pericas, Chem. Sci., 2015, 6,
´
`
-
1510–1515.
ClCuN4O4: C, 29.37; H, 3.70; N, 17.12 found: C, 29.44; H, 14 N. Armaroli, G. Accorsi, F. Cardinali and A. Listorti, Top.
3.75; N, 17.07. IR (in Nujol, n) 2272 (m), 2301 (m) (C^N); 1083
Curr. Chem., 2007, 280, 69–115.
15 M. Mohankumar, M.
(vs), 623 (s) (ClO4) cmꢀ1
.
Holler,
E.
Meichsner,
J.-F. Nierengarten, F. Niess, J.-P. Sauvage, B. Delavaux-
Nicot, E. Leoni, F. Monti, J. M. Malicka, M. Cocchi,
E. Bandini and N. Armaroli, J. Am. Chem. Soc., 2018, 140,
2336–2347.
Conclusions
In conclusion, we elaborated an efficient protocol for the
synthesis of [Cu(CH3CN)4]X complexes (X ¼ BF4ꢀ, PF6ꢀ, ClO4
)
16 A. F. Chaudhry, S. Mandal, K. I. Hardcastle and C. J. Fahrni,
Chem. Sci., 2011, 2, 1016–1024.
ꢀ
using stable, inexpensive and low toxic materials. The protocol
makes possible to carry out the reaction in aqueous media and 17 M. Trose, F. Nahra and C. S. J. Cazin, Coord. Chem. Rev.,
minimizes the amount of toxic acetonitrile in the synthesis.
2018, 355, 380–403.
According to this protocol the targeted complexes could be 18 I. O. Koshevoy, A. J. Karttunen, J. R. Shakirova,
obtained in high yield (82–87%) as pure crystalline material.
A. S. Melnikov, M. Haukka, S. P. Tunik and
T. A. Pakkanen, Angew. Chem., Int. Ed. Engl., 2010, 49,
8864–8866.
Conflicts of interest
19 J. R. Shakirova, E. V Grachova, V. V Gurzhiy, S. K. Thangaraj,
¨
There are no conicts to declare.
J. Janis, A. S. Melnikov, A. J. Karttunen, S. P. Tunik and
I. O. Koshevoy, Angew. Chem., Int. Ed., 2018, 57, 14154–
14158.
20 M. J. Leitl, D. M. Zink, A. Schinabeck, T. Baumann, D. Volz
and H. Yersin, Top. Curr. Chem., 2016, 374, 25.
Acknowledgements
This research has been supported by grant of the Russian
Foundation for Basic Research 16-33-60109. The work was 21 E. Fresta and R. D. Costa, J. Mater. Chem. C, 2017, 5, 5643–
carried out using equipment of the Research park of St.
5675.
15534 | RSC Adv., 2019, 9, 15531–15535
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