10.1002/ejic.201801136
European Journal of Inorganic Chemistry
FULL PAPER
in diethyl ether (10 mL) and stirred at room temperature for 14 h. The
resulting suspension was stored at -28 °C and in addition to a powder
colourless crystals of Na(OEt2)[Al(OC5F4N)4(NMe3)] also formed. The
[1]
a) S. H. Strauss, Chem. Rev. 1993, 93, 927; b) I. Krossing, I. Raabe,
Angew. Chem. Int. Ed. 2004, 43, 2066; Angew. Chem. 2004, 116,
2116; c) E.-X. Chen, S. J. Lancaster in Comprehensive Inorganic
Chemistry II, Elsevier, 2013, p. 707; d) C. Knapp in Comprehensive
Inorganic Chemistry II, Elsevier, 2013, p. 651; e) I. M. Riddlestone, A.
Kraft, J. Schaefer, I. Krossing, Angew. Chem. Int. Ed. 2018, 57, 13982;
Angew. Chem. 2018, 130, 14178.
solid
was
isolated
and
dried
under
vacuum
to
yield
Na[Al(OC5F4N)4(NMe3)]·(0.6OEt2). Yield 0.720 g, 68 %, (ca. 80 % purity).
3
1H NMR (300 MHz, CD3CN, 298 K): δ 3.41 (q, JHH = 7.0 Hz, 4H,
3
OCH2CH3), 2.60 (s, 9H, N(CH3)3), 1.12 (t, JHH = 7.0 Hz, 6H, OCH2CH3).
19F NMR (282 MHz, CD3CN, 298 K): δ –99.8 (br s, o-ArC-F), –165.4 (br s,
m-ArC-F). 27Al NMR (78 MHz, CD3CN, 298 K): δ 17.
[2]
[3]
I. Krossing, A. Reisinger, Coord. Chem. Rev. 2006, 250, 2721.
I. Krossing in Comprehensive Inorganic Chemistry II, Elsevier, 2013, p.
681.
[4]
a) S. Dagorne, D. A. Atwood, Chem. Rev. 2008, 108, 4037; b) A. P. M.
Robertson, P. A. Gray, N. Burford, Angew. Chem. Int. Ed. 2014, 53,
6050; Angew. Chem. 2014, 126, 6162; c) V. S. V. S. N. Swamy, S. Pal,
S. Khan, S. S. Sen, Dalton Trans. 2015, 44, 12903; d) T. A. Engesser,
M. R. Lichtenthaler, M. Schleep, I. Krossing, Chem. Soc. Rev. 2016, 45,
789.
Preparation of NaOC5F4N: To a stirred suspension of NaH (0.273 g,
11.4 mmol) in diethyl ether (10 mL) was slowly added a solution of HO-
C5F4N (2.000 g, 11.9 mmol) in diethyl ether (15 mL) and gas evolution
observed. The reaction mixture was stirred for 14 h and the solid isolated
by filtration and washed with diethyl ether (2 x 10 mL). The solid obtained
was then dried under vacuum at 80 °C. Yield 1.900 g, 88 %. 19F NMR
(282 MHz, CD3CN, 298 K): δ –102.7 (s, o-ArC-F), –173.9 (m, m-ArC-F).
[5]
[6]
a) A. B. A. Rupp, I. Krossing, Acc. Chem. Res. 2015, 48, 2537; b) P.
Wasserscheid, T. Welton, Wiley-VCH, Weinheim, 2008.
a) V. Aravindan, J. Gnanaraj, S. Madhavi, H.-K. Liu, Chem. Eur. J.
2011, 17, 14326; b) K. Xu, Chem. Rev. 2014, 114, 11503; c) A.
Lewandowski, A. Świderska-Mocek, J. Power Sources 2009, 194, 601.
a) E. Y.-X. Chen, T. J. Marks, Chem. Rev. 2000, 100, 1391; b) H. F. T.
Klare, M. Oestreich, Dalton Trans. 2010, 39, 9176; c) Y. Li, M. Cokoja,
F. E. Kühn, Coord. Chem. Rev. 2011, 255, 1541.
Preparation of a Na2(OEt2)2[Al(OC5F4N)5] and Na[Al(OC5F4N)4].OEt2
Mixture: To a stirred –78 °C slurry of NaOC5F4N (0.946 g, 5 mmol) in
diethyl ether (20 mL), was added a solution of AlCl3 (0.162 g, 1.2 mmol)
in diethyl ether (10 mL). The reaction mixture was stirred for 14 h, whilst
slowly attaining room temperature. After filtration, the solvent was
removed in-vacuo and the residue extracted into diethyl ether (3 x 10 mL)
and concentrated. Storage at room temperature afforded a mixture of
colourless crystals of Na2(OEt2)2[Al(OC5F4N)5] and Na[Al(OC5F4N)4].OEt2.
Yield 0.201 g. Crude NMR before crystallisation. 19F NMR (376 MHz,
OEt2, 298 K): δ –95.9 (br s, o-ArC-F), –164.7 (m, m-ArC-F). 27Al NMR
(104 MHz, OEt2, 298 K): δ 41.
[7]
[8]
[9]
A. Martens, P. Weis, M. C. Krummer, M. Kreuzer, A. Meierhöfer, S. C.
Meier, J. Bohnenberger, H. Scherer, I. Riddlestone, I. Krossing, Chem.
Sci. 2018, 9, 7058.
a) I. Raabe, A. Reisinger, I. Krossing, Exp. Green Sustain. Chem., 2009,
p. 131; b) I. Krossing, A. Reisinger, Eur. J. Inorg. Chem. 2005, 1979; c)
A. Bihlmeier, M. Gonsior, I. Raabe, N. Trapp, I. Krossing, Chem. Eur. J.
2004, 10, 5041.
Preparation of Na[B(OC5F4N)4]: A round bottomed flask fitted with a
reflux condenser was charged with NaBH4 (0.107 g, 2.9 mmol) and 4-
HO-C5F4N (2.000 g, 12.0 mmol). Toluene (50 mL) was added and the
[10] I. Krossing, Chem. Eur. J. 2001, 7, 490.
[11] A. Shyamsunder, W. Beichel, P. Klose, Q. Pang, H. Scherer, A.
Hoffmann, G. K. Murphy, I. Krossing, L. F. Nazar, Angew. Chem. Int.
Ed. 2017, 56, 6192; Angew. Chem. 2017, 129, 6288.
resulting suspension refluxed for
5 days. After cooling to room
temperature the solid isolated by filtration and washed with toluene (3 x
10 mL) and dried under vacuum. Yield 1.200 g, 60 %. Recrystallization
from THF resulted in the formation of [Na(THF)2][B(OC5F4N)4]·THF. 19F
NMR (282 MHz, CD3CN, 298 K): δ –96.0 (s, o-ArC-F), –159.6 (m, m-ArC-
F). 11B NMR (96 MHz, CD3CN, 298 K): δ 1.0.
[12] A. Reisinger, N. Trapp, I. Krossing, S. Altmannshofer, V. Herz, M.
Presnitz, W. Scherer, Angew. Chem. Int. Ed. 2007, 46, 8295; Angew.
Chem. 2007, 119, 8445.
[13] I. Krossing, J. Am. Chem. Soc. 2001, 123, 4603.
[14] A. Kraft, J. Beck, G. Steinfeld, H. Scherer, D. Himmel, I. Krossing,
Organometallics 2012, 31, 7485.
Preparation of [Me3NH][B(OC5F4N)4]: To a suspension of NaBH4 (0.115
g, 3.0 mmol) in THF (7 mL), a solution of 4-HO-C5F4N (2.09 g, 12.5
mmol) in THF (10 mL) was added dropwise and gas evolution observed.
Once gas evolution had ceased toluene (20 mL) was added and the
reaction mixture refluxed for 3 days. After cooling to room temperature
the crude reaction mixture was transferred onto [Me3NH]Cl (0.290 g, 3.0
mmol) and stirred for 14 h. The reaction mixture was filtered and the
solvent removed in-vacuo to yield a white solid, which was extracted into
diethyl ether (2 x 10 mL). Concentration of this solution and storage at
room temperature resulted in the formation of colourless crystals of
[Me3NH][B(OC5F4N)4]. Yield 1.220 g, 55 %. 1H NMR (300 MHz, CD3CN,
298 K): δ 6.92 (br s, 1H, NH), 2.80 (s, 9H, N(CH3)3). 19F NMR (282 MHz,
CD3CN, 298 K): δ –96.0 (s, o-ArC-F), –159.6 (m, m-ArC-F). 11B{1H} NMR
(96 MHz, CD3CN, 298 K): δ 1.0.
[15] a) I. Krossing, A. Bihlmeier, I. Raabe, N. Trapp, Angew. Chem. Int. Ed.
2003, 42, 1531; Angew. Chem. 2003, 115, 1569; b) A. J. Lehner, N.
Trapp, H. Scherer, I. Krossing, Dalton Trans. 2011, 40, 1448.
[16] H. Großekappenberg, M. Reißmann, M. Schmidtmann, T. Müller,
Organometallics 2015, 34, 4952.
[17] M. Gonsior, I. Krossing, L. Muller, I. Raabe, M. Jansen, L. van Wullen,
Chem. Eur. J. 2002, 8, 4475.
[18] T. Köchner, N. Trapp, T. A. Engesser, A. J. Lehner, C. Röhr, S. Riedel,
C. Knapp, H. Scherer, I. Krossing, Angew. Chem. Int. Ed. 2011, 50,
11253; Angew. Chem. 2011, 123, 11449.
[19] A. G. Massey, A. J. Park, J. Organomet. Chem. 1964, 2, 245.
[20] a) G. Erker, Dalton Trans. 2005, 1883; b) J. Chen, E. Y.-X. Chen,
Dalton Trans. 2016, 45, 6105; c) T. Belgardt, J. Storre, H. W. Roesky,
M. Noltemeyer, H.-G. Schmidt, Inorg. Chem. 1995, 34, 3821.
[21] G. J. P. Britovsek, J. Ugolotti, A. J. P. White, Organometallics 2005, 24,
1685.
[22] D. S. McGuinness, A. J. Rucklidge, R. P. Tooze, A. M. Z. Slawin,
Organometallics 2007, 26, 2561.
Acknowledgements
[23] Y. Sun, M. V. Metz, C. L. Stern, T. J. Marks, Organometallics 2000, 19,
1625.
IMR acknowledges the Alexander von Humboldt Foundation and
the Freiburg Institute for Advanced Studies (FRIAS) for the
award of Fellowships. We thank Dr. Harald Scherer and Fadime
Bitgül for help with NMR spectroscopy and Dr. Daniel Kratzert
for help with crystallography.
[24] W. Tyrra, S. Aboulkacem, I. Pantenburg, J. Organomet. Chem. 2006,
691, 514.
[25] M. Wiesemann, H.-G. Stammler, B. Neumann, B. Hoge, Eur. J. Inorg.
Chem. 2017, 2017, 4733.
[26] a) J. Huhmann-Vincent, B. L. Scott, G. J. Kubas, Inorg. Chem. 1999, 38,
115; b) S. Basu, N. Arulsamy, D. M. Roddick, Organometallics 2008, 27,
3659; c) J. J. Adams, N. Arulsamy, D. M. Roddick, Organometallics
2009, 28, 1148; d) M. W. Holtcamp, L. M. Henling, M. W. Day, J. A.
Keywords: Weakly Coordinating Anions (WCAs) • Lewis acid •
aluminium • aluminate • borate
8
This article is protected by copyright. All rights reserved.