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mixture was stored at −20 °C for 1 h. The suspension was filtered
using a glass frit, and the resulting white product was washed with
hexanes (3 × 10 mL). The product was dried in vacuo (984 mg, 96%
yield).
ACKNOWLEDGMENTS
■
This material is based upon work supported by the U.S. Army
under Contract/Grant W911NF-11-1-0229, the Office of the
Assistant Secretary of Defense for Research and Engineering,
DoD/NSSEFF Program/Naval Postgraduate School under
Awards N00244-09-1-0012 and N00244-09-1-0071, and the
National Science Foundation under Grant CHE-1149314.
(b) A solution of 2 (200 mg, 0.17 mmol) in dichloromethane (10
mL) was added dropwise to a slurry of silver tetrafluoroborate (32.7
mg, 0.17 mmol) in dichloromethane (10 mL). The solution was stirred
in the dark for 1 h. The resulting mixture was filtered through a Celite
pad in a fritted funnel. The Celite was washed with dichloromethane
(3 × 10 mL). The filtrate was collected and the solvent removed under
vacuum to give a white powder (197 mg, 95% yield). 1H NMR
(400.16 MHz, 25 °C, CD2Cl2): 8.15 (s, 2H), 7.88−7.30 (m, 36 H),
7.05 (t, JH−H = 4 Hz, 2H), 6.80 (m, 2H), 3.57−2.43 (br m, 8H).
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31P{1H} NMR (161.98 MHz, 25 °C, DMSO-d6): δ 47.05 (s, JP−Pt
3110 Hz, 2P). ESIMS (m/z): 1107 [M − 2BF4]2+. Found 1107.
=
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Fully Closed Complex (BArF−)2. A solution of sodium tetrakis[3,5-
bis(trifluoromethyl)phenyl]borate (BArF−) (75 mg, 0.085 mmol) in
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temperature and then filtered using a glass frit. The filtrate was
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solid (109 mg, 90% yield). 1H NMR (400.16 MHz, 25 °C, CD2Cl2): δ
7.70 (s, 16H), 7.54 (s, 8H), 7.48−7.32 (m, 36H), 7.05 (t, JH−H = 4 Hz,
4H), 6.89 (s, 2H), 3.10−2.89 (m, 8H). 31P{1H} NMR (161.98 MHz,
25 °C, DMSO-d6): δ 45.11 (s, JP−Pt = 3119 Hz, 2P).
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+
8H), 1.62−1.54 (m, 16H, N(CH2CH2CH2CH3)4 ), 1.44−1.36 (m,
+
8H, N(CH2CH2CH2+CH3)4 ), 0.99 (t, JH−H = 4 Hz, 12H, N-
(CH2CH2CH2CH3)4 ). 31P{1H} NMR (161.98 MHz, 25 °C,
DMSO-d6): δ 44.45 (br s, JP−Pt = 3551 Hz, 1P), 8.42 (br s, JP−Pt
=
3208 Hz, 1P).
Single Crystal X-ray Diffraction. Crystallographic data (Table
S1) and ORTEP diagram (Figure S1) are displayed in the Supporting
Information. A single crystal was mounted using oil (Infineum V8512)
on a glass fiber. All measurements were made on a CCD area detector
with graphite monochromated Mo Kα radiation. Data were collected
using Bruker APEXII detector and processed using APEX2 from
Bruker. All structures were solved by direct methods and expanded
using Fourier techniques. The non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were included in idealized positions
but not refined. Their positions were constrained relative to their
parent atom.
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ASSOCIATED CONTENT
■
S
* Supporting Information
1
Details of FT-IR and H NMR spectroscopy studies of urea
self-association and substrate association, Job plot, catalytic
studies, crystal structure ORTEP diagram and structure details
(including CIF file), 31P{1H} and 1H NMR spectra of 1, 2, and
1
3, and H NMR spectra of 2(BArF−) and 3(BArF−)2. This
material is available free of charge via the Internet at http://
AUTHOR INFORMATION
■
(27) Jeon, Y.-M.; Heo, J.; Brown, A. M.; Mirkin, C. A. Organo-
metallics 2006, 25, 2729.
(28) Oliveri, C. G.; Gianneschi, N. C.; Nguyen, S. T.; Mirkin, C. A.;
Stern, C. L.; Wawrzak, Z.; Pink, M. J. Am. Chem. Soc. 2006, 128,
16286.
Corresponding Author
Notes
The authors declare no competing financial interest.
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dx.doi.org/10.1021/ja500214r | J. Am. Chem. Soc. 2014, 136, 4689−4696