O.A. Varzatskii et al. / Inorganic Chemistry Communications 14 (2011) 1504–1507
1507
[2] Y.Z. Voloshin, O.A. Varzatskii, A.S. Belov, Z.A. Starikova, K.Y. Suponitsky, V.V.
Novikov, Y.N. Bubnov, Inorg. Chem. 47 (2008) 2155.
[3] O.A. Varzatskii, Y.Z. Voloshin, S.V. Korobko, S.V. Shulga, R. Krämer, A.S. Belov, A.V.
Vologzhanina, Y.N. Bubnov, Polyhedron 28 (2009) 3431.
[4] Y.Z. Voloshin, V.E. Zavodnik, O.A. Varzatskii, V.K. Belsky, A.V. Palchik, N.G.
Strizhakova, I.I. Vorontsov, M.Y. Antipin, Dalton Trans. (2002) 1193.
[5] FeBd2(Cl(Pyz)Gm)(BF)2. Complex FeBd2(Cl2Gm)(BF)2 (0.74 g, 1 mmol) and 2,3-
dimethyl-5,6-dicyanopyrazine (0.16 g, 1 mmol) were dissolved/suspended in THF
(15 ml) and 0.33 M THF solution of cadmium(II) amide Cd[N(Si(CH3)3)2] (6 ml,
2 mmol) was added dropwise to the stirring reaction mixture under argon. The
reaction mixture was stirred overnight and then diluted with 5% aqueous acetic acid.
The product was extracted with dichloromethane (50 ml, in two portions). The
extract was dried with Na2SO4, evaporated to a small volume (approximately 10 ml)
and precipitated with hexane (50 ml). The precipitate was filtered and dissolved in a
small amount of dichloromethane. The dichloromethane solution was filtered
through a silica gel (Silasorb SPH-300, 30-mm layer, eluent: dichloromethane :
hexane 3:1 mixture). The filtrate was evaporated to a small volume (approximately
1 ml) and precipitated with hexane. The precipitate was filtered off, washed with
hexaneand dried in vacuo. Yield: 0.33 g (38%). Anal. Calc. for C38H25N10O6B2F2ClFe: C,
52.55; H, 2.90; N, 16.13; Fe, 6.43; Cl, 4.08. Found (%): C, 52.63; H, 2.65; N, 15.15; Fe,
6.24; Cl, 3.99. 1H NMR (CD2Cl2): δ, ppm: 2.72 (s, 3H, CH3) , 4.51 (s, 2H, CH2), 7.24 (m,
8H, meta-H), 7.26 (m, 4H, para-H), 7.29 (m, 8H, orto-H). 13C{1H} NMR (CD2Cl2) δ,
ppm; J, Hz: 24.23 (s, CH3), 34.48 (s, 2H, CH2), 115.07, 115.24 (s, C=N), 130.07, 130.08
(s, meta-C), 130.84 (s, ipso-C), 132.18 (s, C – C=N) , 132.45, 132.47 (s, para-C),
132.53, 132.56 (s, orto-C), 133.31 (Cl – C=N), 151.85(s, CH2 – C=N), 156.16 (s, CH3
–
C=N), 159.24, 159.46 (s, Ph – C=N), 160.00 (s, CH2 – C=N). MS (MALDI-TOF): m/z
(I, %): 868(55) [M]+•, 891(100) [M+Na+ +•.UV–vis (CH3CN): λmax/nm (ε·10−3
] ,
mol−1 L cm−1) 247 (15), 276 (11), 299 (4.2), 328 (1.3), 372 (1.2), 460 (6.1), 470
(5.7). UV–vis (CH3CN + (C2H5)3N): λmax/nm (ε·10–3, mol−1 L cm−1) 272 (11), 304
(3.7), 379 (4.8), 449 (4.0), 481 (8.0), 531 (5.4), 581 (4.7), 632 (3.2).
[6] X-ray crystallography experiment. The red prismatic crystals of the complex FeBd2
(Cl(Pyz)Gm)(BF)2 · 0.5 CH2Cl2 were grown from its solution in dichloromethane –
benzene – hexane 1:1:5 mixture at room temperature. The crystal system of
C38.5H26B2Cl2F2FeN10O6 (M= 911.06) is triclinic; at 100 K: a =12.933(3),
b=13.735(3), c=14.216(6) Å, α=109.893(10) ° β=99.315(10)° γ=115.617(6),
V=1993.9(11) Å3, space group P1, Z=2, Dcalc=1.517 g cm−3, μ=0.583 mm−1
.
The intensities of 18879 reflections were measured with a Bruker Apex II CCD area
detector using graphite monochromated Mo-Kα radiation (λ=0.71073 Å, 2θb55°).
9078 independent reflections (R(int)=0.0840) were used for the solution and
refinement of the structure. The structure was solved by the direct method and
refined by full-matrix least squares against F2. Non-hydrogen atoms were found on
difference Fourier maps and refined with anisotropic displacement parameters. The
positions of hydrogen atoms were calculated and included in the refinement in
isotropic approximation by the riding model with the Uiso(H)=1.2 eq(C), where
Ueq(C) are equivalent thermal parameters of the parent atoms. The final
convergence factors were R1(F)=0.0661 and wR2=0.1445 for 5184 reflections
with IN2σ(I). Goodness-of-fit (F2)=1.00 for all the reflections included in the last
stage of refinement. All calculations were made using the SHELXTL PLUS 5 program
package [7] CCDC reference number is 819473.
Fig. 3. UV–vis spectra of the clathrochelate FeBd2(Cl(Pyz)Gm)(BF)2 (A) and its
deprotonated form (B).
[7] G.M. Sheldrick, Acta Cryst. A64 (2008) 112.
[8] Y.Z. Voloshin, O.A. Varzatskii, A.V. Palchik, I.I. Vorontsov, M.Y. Antipin, E.G. Lebed,
Inorg. Chim. Acta 358 (2005) 131.
[9] A.B. Burdukov, M.A. Vershinin, N.V. Pervukhina, Y.Z. Voloshin, O.A. Varzatsky,
Russ. Chem. Bull. (2006) 1910.
Supplementary materials related to this article can be found online
[10] A.B. Burdukov, E.G. Boguslavsky, V.A. Reznikov, N.V. Pervukhina, M.A. Vershinin,
Y.Z. Voloshin, O.A. Varzatsky, Y.N. Bubnov, Russ. Chem. Bull. (2005) 1097.
References
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