Organometallics
Article
747.9980, found 748.0035. Anal. Calcd for C19H30BF4I2IrN6 (875.32):
C, 26.07; H, 3.45; N, 9.60. Found: C, 26.37; H, 3.44; N, 9.34.
Synthesis of Complex 3b. Compound 2b (0.15 mmol, 0.14 g)
was dissolved in 20 mL of CH2Cl2, and then HBF4·Et2O (0.16 mmol,
22 μL) was added dropwise at 0 °C. After the addition the reaction
mixture was stirred for 1 h at 0 °C. Subsequently, 10 mL of CH3CN
was added and the reaction mixture was stirred at room temperature
for 1 h. Vacuum evaporation of the volatiles afforded a residue, which
was washed with Et2O (3 × 20 mL) and dried under vacuum to give
the title compound as an orange solid in 87% yield (0.13 mmol, 0.12
g). 1H NMR (acetone-d6 with 30 equiv of CH3CN, 300 MHz): δ 7.67
(d, 2H, JH−H = 2.0 Hz, CHim ext), 7.58 (d, JH−H = 2.0 Hz, CHim int), 7.31
(m, 4H, CHAr‑meta), 7.06 (d, 4H, JH−H = 8.2 Hz, CHAr‑ortho), 6.97 (t,
2H, JH−H = 7.4 Hz, CHAr‑para), 6.65 (s, 2H, NCH2N), 4.95 (m, 4H,
NCH2), 4.52 (m, 4H, OCH2), 2.87 (s, 6H, CH3CN). 13C{1H} NMR
(acetone-d6, 75.5 MHz): δ 159.2 (Cipso), 130.5 (CHAr‑meta), 127.8
(NCimN), 123.8 (CHim ext),123.2 (CH3CN), 123.0 (CHim int), 122.2
(CHAr‑para), 115.4 (CHAr‑ortho), 68.3 (OCH2), 64.5 (NCH2N), 51.7
(NCH2), 3.6 (CH3CN). 19F NMR (acetone-d6, 282 MHz): δ −150.6
ppm. HRMS (ESI): m/z calcd for C25H27I2IrN5O2 (M+ − CH3CN)
875.9874, found 875.9914. Anal. Calcd for C27H30BF4I2IrN6O2
(1003.41): C, 32.32; H, 3.01; N, 8.38. Found: C, 31.51; H, 2.78; N,
7.87.16
ASSOCIATED CONTENT
* Supporting Information
Tables, figures, and CIF files giving X-ray crystallographic
details and additional NMR data. This material is available free
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S
AUTHOR INFORMATION
Corresponding Authors
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the Spanish Ministry of Economy
and Competitiveness (MINECO/FEDER) (CONSOLIDER
INGENIO CSD2009-0050, CTQ2011-27593 projects, and
“Juan de la Cierva” (M.I.) and Ramon y Cajal (P.J.S.M.)
́
programs) and the DGA/FSE-E07. The authors express their
appreciation for support from the Ministry of Higher Education
of Saudi Arabia in establishment of the Center of Research
Excellence in Petroleum Refining & Petrochemicals at King
Fahd University of Petroleum & Minerals (KFUPM) and
support from the KFUPM-University of Zaragoza research
agreement.
Synthesis of Complex 3c. Experimental details for the
preparation of compound 3c, as well as its full characterization, can
be found in the literature.9,10
General Procedure for the Hydrolysis of Silanes. The
reactions were performed on a Man on the Moon series X102 kit
mL placed in an isothermal bath at 298 K.
DEDICATION
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Dedicated to the memory of Prof. Michael F. Lappert, an
outstanding and creative scientist, for his many and diverse
contributions to organometallic chemistry.
In a typical procedure, the reactor was charged with a solution of
the catalyst (0.01 mmol; 8.8 mg of 3a, 9.1 mg of 3b or 8.0 mg of 3c)
and 5 equiv of distilled water (5 mmol, 90 μL) in 2 mL of acetone.
The reactor was closed and the pressure measurement started. Once
the reading of hydrogen pressure stabilized, the corresponding silane
(1.0 mmol; 160 μL of PhMe2SiH, 161 μL of Et3SiH or 134 μL of
(MeO)3SiH) was added with a syringe in one batch. The amount of
H2 generated during the reaction was calculated by means of the ideal
gas law: PV = nRT. At the end of the reaction the reaction mixture was
REFERENCES
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1
analyzed by H NMR.
General Procedure for the Methanolysis of Silanes. The
reactions were performed analogously to the procedure described
above for the hydrolysis of silanes, except that in this case the
corresponding silane was added to a solution of the catalyst (3a, 3b, or
3c) in 2 mL of methanol.
General Procedure for Recycling Experiments. The reactions
were performed analogously to the procedure described above. After
every cycle the system was depressurized and a new 1 equiv of
PhMe2SiH was added. In the case of the hydrolysis experiments 1
equiv of water was previously added to maintain the excess of 5 equiv.
Crystal data for 3a: [C20H31BCl2F4I2IrN6], monoclinic, P21/c, a =
12.2648(8) Å, b = 9.2929(6) Å, c = 26.5659(17) Å, β = 95.5340(10)°,
Z = 4, Mr = 959.22 g mol−1, V = 3013.8(3) Å3, Dcalcd = 2.114 g cm−3,
λ(Mo Kα) = 0.71073 Å, T = 100 K, μ = 6.702 mm−1, 25231 reflections
collected, 7109 reflections observed (Rint = 0.0595), R1(Fo) = 0.0778
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D.; Messerle, B. A.; Rehr, M.; Soler, L. P.; Hambley, T. W.
Organometallics 2003, 22, 2387−2395.
2
(I > 2σ(I)), wR2(Fo ) = 0.1772 (all data), GOF = 1.080. CCDC
1034731.
Crystal data for 3b′: [C25H27BF4I2IrN5O2], monoclinic, P21/n, a
= 15.841(12) Å, b = 12.668(9) Å, c = 16.196(12) Å, β = 116.078(8)°,
Z = 4, Mr = 962.33 g mol−1, V = 2919(4) Å3, Dcalcd = 2.190 g cm−3,
λ(Mo Kα) = 0.71073 Å, T = 100 K, μ = 6.747 mm−1, 32539 reflections
collected, 6775 unique reflections (Rint = 0.0437), 5644 observed,
(3) (a) Garces
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(b) Yu, M.; Jing, H.; Fu, X. Inorg. Chem. 2013, 52, 10741−10743.
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S.-W. K; Kang, S. O. Int. J. Hydrogen Energy 2011, 36, 12305−12312.
2
R1(Fo) = 0.0352 (I > 2σ(I)), wR2(Fo ) = 0.1055 (all data), GOF =
0.998. CCDC 1034732.
G
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