K. Schuhen, D. Sieb, H. Wadepohl, M. Enders
ARTICLE
[M+ – Br], 566 (13) [M+ – 2 × Br]. UV/Vis (THF): λmax (ε,
References
L·mol·cm–1) = 290 (76000), 388 (36000), 562 (11000) nm.
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η5ꢀ(4ꢀBromoꢀ2,1,3ꢀbenzothiadiazolꢀ7ꢀyl)cyclopentadienylchromꢀ
ium(III) dichloride (12): A solution of sodium cyclopentadienide
(555 mg, 6.3 mmol) in THF (60 mL) was added dropwise to 4,7ꢀdiꢀ
bromoꢀ2,1,3ꢀbenzothiadiazole (929 mg, 3.16 mmol) in THF (70 mL).
The reaction mixture was stirred at room temp. for 24 h leading to a
deep blue color. This solution was added slowly through a cannula to
CrCl3(thf)3 (1.18 g, 3.16 mmol) in THF (80 mL). After 2 d at room
temp., the color of the reaction mixture turned intensely green. Reꢀ
moval of the solvent led to a green powder that was washed with
hexane and the product was extracted with toluene. After evaporation
of the solvent, 490 mg (1.22 mmol, 39 %) of the solid green
complex 12 were isolated. 1H NMR (C6D6, 400 MHz): δ = 159 (s,
ν1/2 ≈ 4000 Hz, CHCp), 19 (s, ν1/2 ≈ 500 Hz, CH5), 6.8 (s, ν1/
[2] a) J. Okuda, in Metallocenes (Eds.: A. Togni, R. L. Halterman),
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≈ 18 Hz, CH6). MS (EI): m/z (%) = 364 (25) [M+ – Cl], 329 (100)
2
[M+ – 2 Cl]. MS (HRꢀFAB) C11H6N279Br35ClSCr calcd. 363.8529;
found 363.8555.
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Crystal Structure Determinations
Crystal Data H1: C15H9BrN2S, monoclinic, space group P21, a =
19.1008(14), b = 7.4055(6), c = 19.1311(14) Å, β = 109.462(1)°, V =
2551.5(3) Å3, Z = 8, µ = 3.370 mm–1, F(000) = 1312. T = 100(2) K,
θ range 1.1 to 30.1°. Index ranges h, k, l (independent set): –26 to
26, –10 to 10, –26 to 26. Reflections measd.: 59944, indep.: 14928
[Rint = 0.0448], obsd. [I > 2σ(I)]: 13768. Final R indices [Fo > 4σ(Fo)]:
R(F) = 0.0313, wR(F2) = 0.0620, GooF = 1.018. Pseudoꢀmerohedral
and racemic twin. 7: C28H22Fe2N2, monoclinic, space group P21/c, a =
14.2530(16), b = 7.4496(8), c = 22.8163(19) Å, β = 123.218(5)°, V =
2026.7(4) Å3, Z = 4, µ = 1.452 mm–1, F(000) = 1024. T = 100(2) K,
θ range 1.7 to 32.0°. Index ranges h, k, l (indep. set): –21 to 20, –11
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ate, Organometallics 2007, 26, 554–565.
[6] Many systems fall into this category. Often the Cp bound metal
is already coordinatively saturated. The most prominent examples
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in Metallocenes; A. Togni, R. L. Halterman, Eds.; WileyꢀVCH:
Weinheim, 1998; p 686–721 and ref. cited therein.
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3832–3839.
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Organometallics 1988, 7, 474–476.
[11] Z. Ziniuk, I. Goldberg, M. Kol, J. Organomet. Chem. 1997, 545,
441–446.
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Trans. 1990, 1737–1740; b) M. Munakata, T. KurodaꢀSowa, M.
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[13] P. Fernandez, H. Pritzkow, J. J. Carbo, P. Hofmann, M. Enders,
Organometallics 2007, 26, 4401–4412.
[14] a) G. N. La Mar, W. Horrocks Jr., R. H. Holms (Eds.), NMR of
Paramagnetic Molecules: Principles and Applications, Academic
Press, NY, 1973, ; b) I. Bertini, C. Luchinat, G. Parigi, Solution
NMR of Paramagnetic Molecules, Elsevier, 2001; c) F. H. Köhler,
Magnetism: Molecules to Materials, 2001, p. 379, WileyꢀVCH
Verlag GmbH, Weinheim, Germany.
[15] Gaussian 03, Revision B.03, M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A.
Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M.
Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M.
Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida,
T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.
E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J.
to 0, –34 to 19. Reflections measd.: 34112, indep.: 6945 [Rint
=
0.0645], obsvd. [I > 2σ(I)]: 5121. Final R indices [Fo > 4σ(Fo)]: R(F) =
0.0410, wR(F2) = 0.1081, GooF = 1.058. 8: C24H12N2O6Re2, triclinic,
¯
space group P1, a = 8.0187(16), b = 9.5933(19), c = 15.026(3) Å, α =
71.948(4), β = 123.218(5), γ = 82.969(4)°, V = 1072.8(4) Å3, Z = 2,
µ = 2.467 mm–1, F(000) = 736. T = 150(2) K, θ range 2.2 to 32.2°.
Index ranges h, k, l (indep. set): –11 to 11, –13 to 14, 0 to 22. Reflecꢀ
tions measd.: 28868, indep.: 7906 [Rint = 0.0839], obsvd. [I > 2σ(I)]:
5934. Final R indices [Fo > 4σ(Fo)]: R(F) = 0.0703, wR(F2) = 0.1096,
GooF = 1.002. Pseudoꢀmerohedral twin.
Intensity Data Collection: Bruker AXS Smart 1000 CCD diffractomꢀ
eter, MoꢀKα radiation, graphite monochromator, λ = 0.71073 Å. Strucꢀ
ture solution: conventional direct methods [20, 21] (H1 and 8) or heavy
atom method combined with structure expansion by direct methods
[22] (7). Refinement: fullꢀmatrix leastꢀsquares methods based on F2;
all nonꢀhydrogen atoms anisotropic. Hydrogen atoms were input at
calculated positions and refined riding (H1 and 8) or fully refined (7)
[23, 21]. The twin refinements were against all overlapping and nonꢀ
overlapping reflections. Crystallographic data (excluding structure facꢀ
tors) for the structures reported in this paper have been deposited with
the Cambridge Crystallographic Data Center: CCDCꢀ713319 (H1),
ꢀ713317 (7) and ꢀ713318 (8). These data can be obtained free of charge
Union Road, Cambridge CB2 1EZ, UK; Phone: +44 1223 336408,
Fax: +44 1223 336033; Eꢀmail: deposit@ccdc.cam.ac.uk].
Acknowledgement
This work was supported by the Deutsche Forschungsgemeinschaft
(SFB623).
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© 2009 WileyꢀVCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1560–1567