Inorganic Chemistry
ARTICLE
11B NMR (CDCl3): δ 19.75 (s). Anal. Calcd. for C8H5BF3IO4: C, 26.70;
H, 1.40; I, 35.27. Found: C, 26.55; H, 1.31; I, 34.99.
’ ASSOCIATED CONTENT
S
Supporting Information. Crystallographic information
Single crystals of product 18 suitable for X-ray crystallographic ana-
lysis were obtained by slow evaporation of the chloroform solution
of 18. X-ray diffraction data were collected on a Rigaku RAPID II diffrac-
tometerusinggraphite-monochromatedMoKαradiation(λ= 0.71073 Å)
at 298 K. Multiscan absorption correction was applied to the data using
the CrystalClear 2.0 program (Rigaku Inc. 2010). The structure was
solved by the Patterson method (PATTY) using the CrystalStructure
4.0 program and refined by full-matrix least-squares refinement on F2
using the Crystals for Windows program. Crystal data for 18 C8H5B1F3I1O4:
M 359.83, triclinic, space group P1, a = 5.1165(3), b = 7.9571(5), c =
13.7918(9) Å, α = 90.851(6)o, β = 90.094(6)o, γ = 105.522(7)o, V =
540.95(6) Å3, Z = 2, μ = 3.001 mmÀ1, 13990 reflections measured, 2482
unique; final R1 = 0.0317, Rw = 0.0821. CCDC-836130 contains the
supplementary crystallographic data for compound 18. These data can
html (or from Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, U.K.; fax: (+44) 1223À336À033, or deposit@
ccdc.cam.ac.uk).
b
files (CIF) for compounds 13, 17, 18, and 21. This material is
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: vnemykin@d.umn.edu (V.N.N.), yusubov@mail.ru
(M.S.Y.), vzhdanki@d.umn.edu (V.V.Z.).
’ ACKNOWLEDGMENT
This work was supported by a research grant from the
National Science Foundation (CHE-1009038) and by NSF-
MRI award (MRI-0922366). V.V.Z. and M.S.Y. are also thankful
to the Government of Russia for support of their cooperative
research program on hypervalent iodine chemistry (FCP, GK
02.740.11.5211; Zayavka 2010-1.5-000-010-044 and FCP, GK
11.519.11.5010, Zayavka 2011-1.9-519-024-070).
Preparation of 4-Fluoro-1-trifluoroacetoxy-1H-1λ3-benzo-
[d][1,2,3]iodoxoborol-3-ol (17) by Direct Oxidation of
2-Fluoro-6-iodophenylboronic Acid in Trifluoroacetic Acid.
A solution of 2-fluoro-6-iodophenylboronic acid 11 (0.266 g, 1.0 mmol)
in trifluoroacetic acid (2 mL) was cooled to 5 °C, and the commercial
bleach solution (2.0 mL of ∼5% aqueous NaOCl) was added in 0.1 mL
portions under stirring. The stirring was continued at 5 °C for additional
30 min until complete disappearance of starting material according to
TLC. Then water (5 mL) was added, and the resulting white, crystalline
precipitate was filtered, washed with water, and dried in vacuum to afford
0.292 g (77%) of product 17, mp 139À140 °C (dec), identical to the
sample of 17 prepared by the previous procedure.
Synthesis and Characterization of 4-Fluoro-1-hydroxy-
1H-1λ3-benzo[d][1,2,3]iodoxoborol-3-ol (19). Solid acetate 15
(0.097 g, 0.3 mmol) was mixed with water (2 mL) and NaHCO3
(50 mg) at room temperature. The resulting suspension was stirred
overnight, then the solid was filtered, washed with water, and dried in
vacuum to give 0.057 g (68%) of product 19; mp 138À138.5 °C (dec).
1H NMR (CDCl3): δ 7.81 (m, 2H), 7.33 (ddd, J = 8.5 Hz, 7.5 Hz, 1.0
Hz, 1H); 11B NMR (CDCl3): δ 19.86 (s). Anal. Calcd. for C6H5BFIO3:
C, 25.57; H, 1.79; I, 45.03. Found: C, 25.97; H, 1.32; I, 45.40. Product 19
can be prepared using a similar procedure starting from trifluoroacetate
17 in 97% yield.
X-ray Crystal Structure of Tetrameric 4-Fluoro-1,3-di-
methoxy-1H-1λ3-benzo[d][1,2,3]iodoxoborol (21). Single
crystals of product 21 suitable for X-ray crystallographic analysis were
prepared by slow crystallization from a solution of the trifluoroacetate 17
in methanol at room temprature in the dark during 10 days. X-ray dif-
fraction data were collected on a Rigaku RAPID II diffractometer using
graphite-monochromated MoKα radiation (λ = 0.71073 Å) at 123 K.
Multiscan absorption correction was applied to the data using the Cry-
stalClear 2.0 program (Rigaku Inc. 2010). The structure was solved by
the Patterson method (PATTY) using the CrystalStructure 4.0 program
and refined by full-matrix least-squares refinement on F2 using the
Crystals for Windows program. Crystal data for 21 C32H36B4F4I4O12: M
1239.45, monoclinic, space group C2/c, a = 15.3210(3), b = 13.6647(2),
c = 37.391(3) Å, β = 99.240(7)o, V = 7726.5(7) Å3, Z = 8, μ = 3.306
mmÀ1, 24417 reflections measured, 8610 unique; final R1 = 0.0393,
Rw = 0.0753. CCDC-836133 contains the supplementary crystallographic
data for compound 21. These data can be obtained free of charge via
tallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.;
fax: (+44) 1223À336À033, or deposit@ccdc.cam.ac.uk).
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