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added to the structure models on calculated positions and were
refined as riding atoms.
Crystal Data for 1: C7H4N4Cl4,
M = 285.94, yellow block,
0.15 × 0.15 × 0.12 mm, monoclinic, P21/c, a = 11.605(4), b = 8.168(3),
c = 11.793(4) Å, ꢀ = 106.434(4)°, V = 1072.2(6) Å3, Z = 4, 2θmax 58.0°,
μ = 1.072 mm–1, T = 100(2) K, 6513 measured reflections, 2567
independent reflections (Rint = 0.037), 1617 observed reflections
[I ≥ 2σ(I)], all independent reflections used in refinement against
|F2|, R = 0.0391, wR = 0.1048, Rall = 0.0837, wRall = 0.134.
Complex 4: Compound [2]I (50 mg, 0.12 mmol) was dissolved in
CH3CN (10 mL) and NaOAc (19 mg, 0.23 mmol) was added to the
solution. The reaction mixture was then stirred for 10 min. Subse-
quently, [{Cp*IrCl(μ-Cl)}2] (46 mg, 0.058 mmol) was added. The re-
sulting suspension was stirred for 4 h at 75 °C. Thereafter, the mix-
ture was filtered through Celite to give a clear solution. The filtrate
was concentrated to about 1 mL, and cold diethyl ether (5 mL) was
added to precipitate a red solid. The solid was isolated by filtration,
washed with diethyl ether (3 × 10 mL) and dried in vacuo, yield
Crystal Data for 5: C24H23N4BrCl4FIr, M = 800.37, yellow prism,
0.20 × 0.15 × 0.15 mm, monoclinic, P21/c, a = 15.718(2), b =
14.800(2), c = 12.474(2) Å, ꢀ = 112.691(2)°, V = 2677.3(6) Å3, Z = 4,
2θmax 59.0°, μ = 6.907 mm–1, T = 100(2) K, 29244 measured reflec-
tions, 7020 independent reflections (Rint = 0.0444), 5904 observed
reflections [I ≥ 2σ(I)], all independent intensities used in refinement
against |F2|, R = 0.0275, wR = 0.0597, Rall = 0.0366, wRall = 0.0628.
1
63 mg (0.084 mmol, 70 %). H NMR (400 MHz, CD2Cl2): δ = 6.03 (d,
CCDC 1486012 (for 1) and 14866013 (for 5) contain the supplemen-
2
2JH,H = 12.9 Hz, 1 H, H4a), 5.25 (d, JH,H = 12.9 Hz, 1 H, H4b), 3.79 (s,
3 H, H8), 1.93 ppm (s, 15 H, H10). 13C{1H} NMR (100 MHz, CD2Cl2):
δ = 155.1 (C1), 142.9 (C5), 128.0 (C6), 117.9 (C3), 115.3 (C2), 110.1
(C7), 94.0 (C9), 56.4 (C4), 39.8 (C8), 10.5 ppm (C10). HRMS (ESI, posi-
tive ions): m/z = 752.9162 (calcd. for [4 + H]+ 752.9166).
Acknowledgments
This work was supported by the Deutsche Forschungsgemein-
schaft (DFG) (IRTG 1444, SFB 858).
Keywords: Homogeneous catalysis · Reduction · Carbene
ligands · Iridium · Chelates
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6.07 (d, 2JH,H = 12.3 Hz, 1 H, H4a), 5.65 (br. s, 2 H, H8), 5.24 (d, 2JH,H
=
12.3 Hz, 1 H, H4b), 1.75 ppm (s, 15 H, H16). 13C{1H} NMR (100 MHz,
1
CD2Cl2): δ = 160.1 (d, JC,F = 246.7 Hz, C10), 158.8 (C1), 144.4 (C5),
3
3
129.8 (d, JC,F = 8.5 Hz, C12), 128.8 (d, JC,F = 3.2 Hz, C14), 126.1
(C6), 124.4 (d, 4JC,F = 3.7 Hz, C13), 123.3 (d, 2JC,F = 12.9 Hz, C9), 117.9
(C3), 116.3 (C2), 115.3 (d, 2JC,F = 21.8 Hz, C11), 109.5 (C7), 93.6 (C15),
56.5 (C4), 48.5 (C8), 9.8 ppm (C16). HRMS (ESI, positive ions): m/z =
800.9496 (calcd. for [5 + H]+ 800.9506) and m/z = 822.9323 (calcd.
for [5 + Na]+ 822.9331).
X-ray Crystallography: X-ray diffraction data were collected with a
Bruker APEX-II CCD diffractometer by using graphite-monochro-
mated Mo-Kα radiation (λ = 0.71073 Å). Empirical absorption correc-
tions by means of the program SADABS[23] were applied to the raw
data for 1 (0.704 ≤ T ≤ 0.879) and 5 (0.164 ≤ T ≤ 0.242). Structure
solutions were found with SHELXS[24] in both cases, and the refine-
ment was carried out with SHELXL[24] by using anisotropic thermal
parameters for all non-hydrogen atoms. Hydrogen atoms were
Eur. J. Inorg. Chem. 0000, 0–0
5
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