´ ˇ
M. Leboschka, M. Sieger, B. Sarkar, M. Niemeyer, T. Schurr, J. Fiedler, S. Zalis, W. Kaim
ARTICLE
man, T. M. Cocker, R. J. Butcher, Eur. J. Inorg. Chem. 2005,
1114.
less psbi were isolated. C14H12N2Se (287.22): calcd. C 58.54, H
4.21, N 9.75; found C 58.29, H 4.46, N 9.57. H NMR (CD3CN):
1
[2] a) S. Dey, V. K. Jain, S. Chaudhury, A. Knoedler, F. Lissner,
W. Kaim, J. Chem. Soc., Dalton Trans. 2001, 723; b) S. Dey, V.
K. Jain, A. Knödler, A. Klein, W. Kaim, S. Zalis, Inorg. Chem.
2002, 41, 2864; c) S. Dey, L. B. Kumbhare, V. K. Jain, T.
Schurr, W. Kaim, A. Klein, F. Belaj, Eur. J. Inorg. Chem.
2004, 4510.
[3] a) C. Jacob, G. I. Giles, N. M. Giles, H. Sies, Angew. Chem.
2003, 115, 4890; Angew. Chem. Int. Ed. 2003, 42, 4742;
b) W.-W. du Mont, G. Mugesh, C. Wismach, P. G. Jones, An-
gew. Chem. 2001, 113, 2547; Angew. Chem. Int. Ed. 2001, 40,
2486.
[4] H. Engelberg-Kulka, R. Schoulaker-Schwarz, Trends Biochem.
Sci. 1988, 13, 419.
[5] a) G. Roelfes, D. Hilvert, Angew. Chem. 2003, 115, 2377; An-
gew. Chem. Int. Ed. 2003, 42, 2275; b) G. N. Schrauzer, Adv.
Food Nutr. Res. 2003, 47, 73.
δ ϭ 4.30 (s, JSe-H ϭ 6.9 Hz), 7.18Ϫ7.10 (m), 7.30Ϫ7.18 (m),
7.60Ϫ7.40 (m). 13C NMR (CD3CN): δ ϭ 24 (JSe-C ϭ 30 Hz), 115.7,
122.9, 128.3, 130.1, 133.7, 143.3, 153.1, 153.8. 77Se NMR
(CD3CN): δ ϭ 351.7.
[Ag(psbi)2](BF4) (1): AgBF4 (17.0 mg, 0.087 mmol) and psbi
(50.0 mg, 0.174 mmol) were dissolved in acetonitrile (5 mL). Color-
less crystals were obtained by storing the solution in a dark place
until the solvent had evaporated. 53 mg (79 %) were isolated.
C28H24AgBF4N4Se2 ·H2O (787.12): calcd. C 42.73, H 3.33, N 7.12;
found C 42.20, H 3.65, N 7.42. 1H NMR (CD3CN): δ ϭ 4.43 (s,
JSe-H ϭ 6.9 Hz), 7.32Ϫ7.28 (m), 7.36Ϫ7.32 (m), 7.6Ϫ7.5 (m), 7.85
s. 13C NMR (CD3CN): δ ϭ 25.9 (JSe-C ϭ 30 Hz), 118.6, 124.4,
127.7, 129.1, 129.5, 130.1, 130.3, 132.5, 133.9, 153.4, 182.7. 77Se
NMR (CD3CN): δ ϭ 330.1.
[6] M. Albrecht, K. Hübler, S. Zalis, W. Kaim, Inorg. Chem. 2000,
39, 4731.
[CuCl2(psbi)2] (2): CuCl2 (11.5 mg, 0.087 mmol) was dissolved in
methanol (3 mL) and mixed with psbi (50.0 mg, 0.174 mmol), also
dissolved in methanol (3 mL). Green crystals (42 mg, 70 %) were
obtained by overlaying the solution with of ethyl ether (15 mL) at
Ϫ18 °C. C28H24Cl2CuN4Se2 (708.89): calcd. C 47.44, H 3.41, N
[7] a) J. Rall, E. Waldhör, B. Schwederski, M. Schwach, S.
Kohlmann, W. Kaim, in Bioinorganic Chemistry: Transition
Metals in Biology and their Coordination Chemistry (Ed.: A. X.
Trautwein), VCH, Weinheim (Germany), 1997, p. 476; b) M.
Albrecht, K. Hübler, T. Scheiring, W. Kaim, Inorg. Chim. Acta
1999, 287, 204; c) W. Kaim, M. Wanner, A. Knödler, S. Zalis,
Inorg. Chim. Acta 2002, 337, 163.
7.90; found C 46.33, H 3.41, N 7.75. UV/Vis (CH3CN): λmax
760 nm. EPR (MeOH, 110 K): gʈ ϭ 2.31, g֊ ϭ 2.065, Aʈ
14.8 mT.
ϭ
ϭ
[8] M. Albrecht, K. Hübler, W. Kaim, Z. Anorg. Allg. Chem. 2000,
626, 1033.
[Cu(psbi)2](BF4) (3): [Cu(CH3CN)4](BF4) (27.3 mg, 0.087 mmol)
and psbi (50.0 mg, 0.174 mmol) were dissolved under argon in
acetonitrile (5 mL). Hexane (15 mL) was added to precipitate
51 mg (0.07 mmol, 80 %) of colorless [Cu(psbi)2](BF4).
C28H24BCuF4N4Se2 ·0.5H2O (733.97): calcd. C 45.83, H 3.44, N
7.64; found C 45.71, H 3.75, N 8.01. 1H NMR (CD3CN): δ ϭ 4.36 s
(JSe-H ϭ 6.9 Hz), 7.28Ϫ7.17 (m), 7.35Ϫ7.28 (m), 7.47Ϫ7.39 (m),
7.60Ϫ7.53 (m). 13C NMR (CD3CN): δ ϭ 26.0 (JSe-C ϭ 30 Hz),
117.8, 124.4, 129.0, 129.6, 130.0, 133.5, 163.5, 186.0.
[9] J. Rall, M. Wanner, M. Albrecht, F. M. Hornung, W. Kaim,
Chem. Eur. J. 1999, 5, 2802.
´ ˇ
[10] M. Leboschka, M. Sieger, M. Niemeyer, S. Zalis, W. Kaim, Z.
Anorg. Allg. Chem. 2008, 634, 2343.
[11] a) M. Mure, Acc. Chem. Res. 2004, 37, 131; b) R. Medda, A.
Padiglia, A. Bellelli, J. Z. Pedersen, A. Finazzi Agro, G. Floris,
FEBS Lett. 1999, 453, 1; c) R. Medda, A. Mura, S. Longu,
R. Anedda, A. Padiglia, M. Casu, G. Floris, Biochimie 2006,
88, 827.
[12] For the effect of thioethers in stabilizing the CuI/CuII transition
see: a) D. B. Rorabacher, Chem. Rev. 2004, 104, 651; b) S. Tor-
elli, C. Belle, C. Philouze, J.-L. Pierre, W. Rammal, E. Saint-
Aman, Eur. J. Inorg. Chem. 2003, 2452.
DFT Calculation of [Ag(psbi)2]؉: The ground state electronic struc-
ture calculation has been done by the density-functional theory
(DFT) method using the ADF2007.01 program package [26Ϫ28].
Slater type orbital (STO) basis sets of triple-ζ quality with two
polarization functions for C, N, Se and Ag and double-ζ quality
with one polarization function for H were employed. The inner
shells were represented by the frozen core approximation (1s for C,
N, 1sϪ3p for Se and 1sϪ3d for Ag were kept frozen). The calcu-
lations were done with the functional including Becke’s gradient
correction [29] to the local exchange expression in conjunction with
Perdew’s gradient correction [30] to the local correlation (ADF/
BP). The scalar relativistic (SR) zero order regular approximation
(ZORA) was used within this study. Geometry optimization was
done without any symmetry constraints.
[13] a) S. Alvarez, P. Alemany, D. Casanova, J. Cirera, M. Llunell,
D. Avnir, Coord. Chem. Rev. 2005, 249, 1693; b) I. Persson, K.
B. Nilsson, Inorg. Chem. 2006, 45, 7428; c) S. Ekici, M. Nieger,
R. Glaum, E. Niecke, Angew. Chem. 2003, 115, 451; Angew.
Chem. Int. Ed. 2003, 42, 435.
[14] K. Paraskevopoulos, M. Sundararajan, R. Surendran, M. A.
Hough, R. R. Eady, I. H. Hillier, S. S. Hasnain, Dalton Trans.
2006, 3067.
[15] a) L. Zhou, D. Powell, K. M. Nicholas, Inorg. Chem. 2006, 45,
3840; b) L. Q. Hatcher, D.-H. Lee, M. A. Vance, A. E. Milli-
gan, R. Sarangi, K. O. Hodgson, B. Hedman, E. I. Solomon,
K. D. Karlin, Inorg. Chem. 2006, 45, 10055; c) N. W. Aboelella,
B. F. Gherman, L. M. R. Hill, J. T. York, N. Holm, V. G.
Young Jr., C. J. Cramer, W. B. Tolman, J. Am. Chem. Soc. 2006,
128, 3445.
[16] S. T. Prigge, B. A. Eipper, R. E. Mains, L. M. Amzel, Science
2004, 304, 864.
[17] a) A. V. Davis, T. O’Halloran, Nat. Chem. Biol. 2008, 4, 148;
b) C. Belle, W. Rammal, J.-L. Pierre, J. Inorg. Biochem. 2005,
99, 1929.
[18] a) M. Afzaal, D. J. Crouch, P. O’Brien, J. Raftery, P. J. Skabara,
A. J. P. White, D. J. Williams, J. Mater. Chem. 2004, 14, 233;
b) D. L. Castro, S. G. Bailey, R. P. Rafaelle, K. K. Banger, A.
F. Hepp, Chem. Mater. 2003, 15, 3142; c) J. J. Vittal, M. T. Ng,
Acc. Chem. Res. 2006, 39, 869.
Acknowledgement
This work was supported by the Deutsche Forschungsgemeinschaft
(SFB 706), the Fonds der Chemischen Industrie, the European Union
(EU) (COST D35), the Grant Agency of the Academy of Sciences
of the Czech Republic (KAN 100400702) and the Ministry of
Education of the Czech Republic (Grant COST OC 139).
References
[19] H.-B. Kraatz, H. Jacobsen, T. Ziegler, P. M. Boorman, Or-
ganometallics 1993, 12, 76.
[20] W. Kaim, J. Biol. Inorg. Chem. 2007, 12, 121 (Suppl. I, 2007).
[1] a) S. G. Murray, F. R. Hartley, Chem. Rev. 1981, 81, 365; b)
A. Panda, S. C. Menon, H. B. Singh, C. P. Morley, R. Bach-
1006
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