Journal of Inorganic and General Chemistry
www.zaac.wiley-vch.de
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
flections unique 8060 [Rint = 0.0579], reflections with I Ͼ 2σ(I) 5460, Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
number of parameters 386, GoF = 0.978, R = 0.0394 (0.0619 all data), of the data can be obtained free of charge on quoting the depository
wR = 0.1032 (0.1109 all data), largest diff. peak and hole 0.59 / –0.93
1
2
numbers CCDC-1057428 (2·MeCN) CCDC-1057429 (3), and
CCDC-1057430 (4·7MeCN) (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
–
3
e·Å .
Crystallographic Data for 4·7MeCN:
152 4
C H132Cu10N O22Si12·
7
C
2
H
3
N, M = 3626.6, monoclinic, crystal color and habit: green
block, size 0. 13ϫ0.22ϫ0.31 mm, P2 /c, a = 17.0473(5) Å, b =
94.393(3)°,
r
Supporting Information (see footnote on the first page of this article):
Details with regard to the identification of the cyclic polysiloxanes and
crystallographic information.
1
29.0522(11) Å,
c
=
33.3880(11) Å,
β
=
V
=
3
–3
–1
1
6487.2(10) Å , Z = 4, ρ = 1.461 g·cm , μ = 1.419 mm , Mo-K
α
radiation (λ = 0.71073 Å), T = 100(2) K, Θ = 3.13–25.19°, F(000) =
7
0
440, reflections collected 970228, reflections unique 28417 [Rint
.1179], reflections with I Ͼ 2σ(I) 15037, number of parameters 1910,
= 0.0708 (0.1394 all data), wR = 0.1479 (0.1722 all
=
Acknowledgements
GoF = 0.933, R
data), largest diff. peak and hole 1.41 / –0.90 e·Å .
1
2
We are grateful to the Humboldt-Universität zu Berlin and the Cluster
of excellence “Unifying concepts in catalysis” for funding. We would
like to thank B. Braun and S. Mebs for helpful discussion.
–3
Crystallographic details are summarized in the Supporting Infor-
mation.
Synthesis of Compound 2: Compound 1 (90 mg, 42 μmol) was dis- References
solved in THF (15 mL), and 2,2Ј-bipyridine (26 mg, 166 μmol) was
[
[
[
1] J. S. Woertink, P. J. Smeets, M. H. Groothaert, M. A. Vance, B. F.
Sels, R. A. Schoonheydt, E. I. Solomon, Proc. Natl. Acad. Sci.
USA 2009, 106, 18908–18913.
2] P. J. Smeets, R. G. Hadt, J. S. Woertink, P. Vanelderen, R. A.
Schoonheydt, B. F. Sels, E. I. Solomon, J. Am. Chem. Soc. 2010,
added. It was stirred overnight and the resulting suspension was fil-
tered. Subsequently all volatiles were removed under reduced pressure,
and the resulting brown residue was recrystallized from THF/n-hexane/
acetonitrile (2:2:5). Within a few days green-blue, block shaped crys-
tals of 2·MeCN were obtained with a yield of 30 mg (46 μmol, 28%
132, 14736–14738.
2–
–1
referred to L ). C34
1 2 3 2 3
H28Cu N O Si (NCCH )0.25 (642.58 g·mol ): C
3] P. Vanelderen, R. G. Hadt, P. J. Smeets, E. I. Solomon, R. A.
64.49 (calcd. 64.48); H 4.85 (calcd. 4.51); N 4.88% (calcd. 4.90%).
Schoonheydt, B. F. Sels, J. Catal. 2011, 284, 157–164.
IR (KBr): ν˜ = 3061 (m), 3041 (m), 1955 (w), 1609 (m), 1601 (m), [4] F. Schax, B. Braun, C. Limberg, Eur. J. Inorg. Chem. 2014, 2124–
1
9
466 (m), 1448 (m), 1306 (m), 1113 (s), 1038 (s), 1018 (s), 999 (s),
74 (s), 944 (s), 770 (s), 732 (s), 703 (s), 528 (s), 493 (m) cm .
2130.
–
1
[5] F. Schax, C. Limberg, C. Mügge, Eur. J. Inorg. Chem. 2012,
4
661–4668.
[6] W.-G. Yuan, Y.-J. Chen, J.-H. Chen, Inorg. Chem. Commun. 2009,
2, 1197–1199.
7] R. C. Bott, P. C. Healy, D. S. Sagatys, Chem. Commun. 1998,
403–2404.
Synthesis of Compound 3: Compound 1 (90 mg, 42 μmol) was dis-
solved in THF (15 mL), and 2,2Ј-bipyridine (26 mg, 166 μmol) was
added. The solution immediately changed color from colorless to red
brown. It was stirred for a couple of minutes, and subsequently all
volatiles were removed under reduced pressure. The red brown residue
was recrystallized from an acetonitrile/diethyl ether solution. Beside
green-blue crystals of compound 2, also small quantities of red crystals
1
[
[
[
2
8] D. J. Darensbourg, M. W. Holtcamp, B. Khandelwal, K. K. Klaus-
meyer, J. H. Reibenspies, Inorg. Chem. 1994, 33, 2036–2040.
9] D. P. Goldberg, A. Caneschi, S. J. Lippard, J. Am. Chem. Soc.
1993, 115, 9299–9300.
could be obtained and identified as compound 3 via X-ray diffraction. [10] L. F. Jones, G. Rajaraman, J. Brockman, M. Murugesu, E. C.
The crystals could not be separated in sufficient amounts to perform
further analyses.
Sanudo, S. J. Teat, W. Wernsdorfer, G. Christou, E. K. Brechin,
D. Collison, Chem. Eur. J. 2004, 10, 5180–5194.
11] M. Manoli, R. D. L. Johnstone, S. Parsons, M. Murrie, M. Af-
fronte, M. Evangelisti, E. K. Brechin, Angew. Chem. 2007, 119,
4540–4544.
[
Synthesis of Compound 4: Compound 1 (220 mg, 102 μmol) was
dissolved in acetonitrile (15 mL) and afterwards the resulting solution
was immediately treated with an excess of dioxygen yielding a green [12] S. Nayak, M. Evangelisti, A. K. Powell, J. Reedijk, Chem. Eur.
J. 2010, 16, 12865–12872.
suspension. Without further workup this suspension was stored for
[
[
[
13] T. C. Stamatatos, K. M. Poole, K. A. Abboud, W. Wernsdorfer,
T. A. O’Brien, G. Christou, Inorg. Chem. 2008, 47, 5006–5021.
14] S. M. Taylor, R. D. McIntosh, J. Rezé, S. J. Dalgarno, E. K. Bre-
chin, Chem. Commun. 2012, 48, 9263–9265.
15] J. Utko, A. B. Canaj, C. J. Milios, M. Soboci n´ ska, T. Lis, Inorg.
Chem. Commun. 2014, 45, 71–74.
crystallization. Dark green block shaped crystals of 4·7MeCN could
be isolated after one week with a yield of 60 mg (18 μmol, 27% re-
2–
–1
ferred to L ). C144
4.55 (calcd. 54.57); H 3.88 (calcd. 3.90); N 0.65% (calcd. 0.86%).
IR (KBr): ν˜ = 3071 (m), 1962 (w), 1898 (w), 1823 (w), 1592 (s), 1429
3
H120Cu10O22Si12(NCCH )1.5 (3236.54 g·mol ): C
5
(
7
s), 1130 (s), 1074 (s), 1035 (s), 1016 (s), 995 (s), 869 (m), 741 (m), [16] T. Hosokawa, M. Takano, S.-I. Murahashi, J. Am. Chem. Soc.
–1
62 (m), 698 (s), 524 (w), 511 (m), 487 (m) cm .
1996, 118, 3990–3991.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Received: April 23, 2015
Published Online: June 23, 2015
Z. Anorg. Allg. Chem. 2015, 2060–2064
2064
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim