2ꢀOrganoselenomethylꢀ1Hꢀbenzimidazole Complexes of Copper(II) and Copper(I)
(81 mg, 0.268 mmol) were mixed under argon in CH3CN (10 mL), Crystallographic data have been deposited with the Cambridge Crystalꢀ
stirred for 2 hours. Afterwards, the solvent was slowly removed to lographic Data Centre, CCDCꢀ722404, ꢀ722405, ꢀ722406, ꢀ722407,
obtain the sensitive product. Yield: 72 mg (66 %). Anal and ꢀ722408. Copies of the information may be obtained free of charge
C30H28CuF6N4PSe2 (811.01 g·mol–1): calcd. C 44.43; H 3.48; N from: The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
1
6.91 %; found: C 43.94; H 3.25; N 7.05 %. H NMR (CD3CN): δ = UK (Fax: +44ꢀ1223ꢀ336ꢀ033; EꢀMail: deposit@ccdc.cam.ac.uk; www:
3.73 (s, CH3), 4.42 (s, CH2), J(CH2–77Se 6.9 Hz); 7.14–7.58 (m, CH). http://www.ccdc.cam.ac.uk).
13C NMR (CD3CN): δ = 23.4 (CH2), J(13Cꢀ77Se 30 Hz); 30.5 (CH3),
110.7, 118.1, 123.1, 123.6, 128.2, 128.6, 129.2, 129.4, 129.6, 135.9,
155.2. 77Se NMR (CD3CN): δ = 309.
DFT Calculations
Ground state electronic structure calculations of the complex ions
[Cu(mmb)2]+ and [Cu(mpsbi)2]+ (see Figure 8) were performed by the
densityꢀfunctional theory (DFT) method using ADF2007.1 [26–28].
Slater type orbital (STO) basis sets of tripleꢀζ quality with two polariꢀ
zation functions for sulfur, selenium, and copper and tripleꢀζ quality
with one polarization function for the other atoms were employed. The
inner shells were represented by the frozen core approximation (1s for
C, N, 2p for S, 3p for Se and 1s–2p for Cu were kept frozen). The
following density functionalisms were used within ADF: The local
density approximation (LDA) with VWN parameterization of electron
gas data or the functional including Becke’s gradient correction [29]
to the local exchange expression in conjunction with Perdew’s gradient
correction [30] to the LDA expression (ADF/BP). The scalar relativisꢀ
tic (SR) zero order regular approximation (ZORA) was used within
this study. Geometry optimizations were done without any symmetry
constraints.
[Cu(msbi)2](PF6) = [5](PF6): The precursor [Cu(CH3CN)4](PF6)
(50 mg, 0.134 mmol) and the ligand msbi (60 mg, 0.268 mmol) were
stirred in CH3CN (10 mL) for 2 hours. Afterwards, the solvent was
slowly removed to obtain the very sensitive product. Yield: 68 mg
(72 %). Anal C18H20CuF6N4PSe2 (658.81 g·mol–1): calcd. C 32.82; H
3.06; N 8.51 %; found: C 32.78; H 2.97; N 9.10 %. 1H NMR
(CD3CN): δ = 2.11 (s, CH3), 4.05 (s, CH2); 7.28–7.62 (m, CH). 13C
NMR (CD3CN): δ = 6.3 (CH3), 21.3 (CH2), 30.5 (CH3), 115.1, 123.1,
129.7, 154.8.
[Cu(mpsbi)2](BF4)
=
[3](BF4):
A
solution of mpsbi (83 mg,
solution of
0.28 mmol) in MeOH (3 mL) was treated with
a
Cu(BF4)2·6H2O (48 mg, 0.14 mmol) in MeOH (3 mL). The darkꢀgreen
solution was stirred for one day. Afterwards, the solvent volume was
reduced to 50 % and a green solid precipitated by cooling to 4 °C.
Redissolving in dry MeOH and keeping at 4 °C produced colorless
1
crystals (rods) suitable for Xꢀray diffraction. Yield: 12 mg (11 %). H
NMR (CDCl3): δ = 3.71 (s, CH3), 4.45 (s, CH2), 7.15–7.70 (m, CH).
Acknowledgement
[Cu(psbi)2](PF6)
=
[4](PF6):
The
precursor
compound
This work was supported by the Deutsche Forschungsgemeinschaft
(SFB 706), the Fonds der Chemischen Industrie, the 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 Repub
lic (Grant COST OC 139).
[Cu(CH3CN)4](PF6) (50 mg, 0.134 mmol) and the ligand psbi (77 mg,
0.268 mmol) were mixed under argon in CH3CN (10 mL), stirred for
2 hours, and the solvent was slowly removed to yield 87 mg (83 %)
of the product. Anal C28H24CuF6N4PSe2 (782.95 g·mol–1): calcd. C
42.95; H 3.09; N 7.16 %; found: C 42.56; H 3.45; N 6.86 %. 1H NMR
(CD3CN): δ = 4.39 (s, CH2), 7.18–7.60 (m, CH). 13C NMR (CD3CN):
δ = 26.0, 117.8, 124.4, 129.0, 129.6, 130.0, 133.5, 163.5, 186.0. Crysꢀ
tallization at –18 °C of an acetonitrile solution produced single crystals
of [CuI(psbi)2][CuI(psbi)(psbiꢀH+)](PF6)·CH3CN = [4][4'](PF6)·CH3CN.
Anal. C58H50Cu2F6N9PSe4 (1462.901 g·mol–1): calcd. C 47.68; H 3.45;
N 8.63 %, found: C 47.58; H 3.54; N 8.66 %.
References
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Crystal Structure Determination
Colorless single crystals of [3](BF4) were obtained from a methanol
solution at 4 °C. Green single crystals of [2](BF4)2 were grown by
slow diffusion of diethyl ether into a methanol solution. Data for both
crystals were collected at 293 K with a NONIUS Kappa CCD diffracꢀ
tometer. Green single crystals of [1]Cl·2MeOH were obtained by slow
evaporation from a saturated methanol solution, single crystals of
[4][4'](PF6)·CH3CN were obtained from a concentrated acetonitrile soꢀ
lution, and single crystals of msbi were grown from an ethyl acetate/
petroleum ether (1:1) mixture by slow evaporation at room temperaꢀ
ture. Data collection for these crystals was performed at 173 K (msbi,
[4][4'](PF6)·CH3CN) and 293 K ([1]Cl·2 MeOH) with a Siemens P4
diffractometer employing the ωꢀ2θ scan technique. The structures were
solved by direct methods using the SHELXTL package [25], and reꢀ
finement was carried out with SHELXL97 employing fullꢀmatrix leastꢀ
[7] a) J. Rall, E. Waldhör, B. Schwederski, M. Schwach, S. Kohlꢀ
mann, W. Kaim, in Bioinorganic Chemistry: Transition Metals in
Biology and their Coordination Chemistry, (Ed.: A. X. Trautꢀ
wein), 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.
2
2
squares methods on F2 with Fo ≥ 2σ (Fo ). All nonꢀhydrogen atoms
were treated anisotropically; hydrogen atoms were included by using
appropriate riding models. Additional crystallographic information is
given in Table 1.
Z. Anorg. Allg. Chem. 2009, 2177–2184
© 2009 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim
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