M. Beller et al.
1
91, 77, 58, 42; HRMS: m/z: calcd for C23H25N: 315.1987; found: 315.1968
[M +].
91%; H NMR (400 MHz, 233 K, [D8]THF): d = 7.16–7.11 (m, 4H), 4.44
(m, 2H), 3.35 (m, 2H), 2.43–2.38 (m, 12H), 2.06 (s, 6H), 1.78–1.70 ppm
(m, 8H); 13C NMR (100 MHz, 233 K, [D8]THF): d = 187.9 (d, JRh,C
=
N-(3,3-Diphenylpropyl)-2,3-dihydro-1H-indole: Yield: 86%; 1H NMR
(400 MHz, CDCl3): d = 7.22–6.89 (m, 10H), 6.56–6.19 (m, 4H), 4.01 (t,
J=7.7 Hz, 1H), 3.23 (t, J=8.3 Hz, 2H), 2.93–2.89 (m, 2H), 2.84 (t, J=
8.3 Hz, 2H), 2.26 ppm (m, 2H); 13C NMR (100 MHz, CDCl3): d = 152.3,
144.5, 129.9, 128.4, 127.8, 127.2, 126.2, 124.3, 117.5, 107.1, 53.1, 48.4, 47.7,
32.9, 28.6 ppm; GC-MS (EI, 70 eV): m/z: 313 [M +], 234, 165, 132, 91, 77,
51, 27; elemental analysis calcd (%) for C23H23N: C 88.13, H 7.40, N 4.47;
found: C 88.15, H 6.94, N 4.42.
N-(3,3-Diphenylpropyl)-4-pyridin-2-yl-piperazine: Yield: 87%; 1H NMR
(400 MHz, CDCl3): d = 8.44–6.82 (brm, 4H), 7.70–7.41 (m, 10H), 4.28
(t, J=6.9 Hz, 1H), 3.78 (t, J=4.9 Hz, 4H), 2.75 (t, J=4.9 Hz, 4H), 2.62–
2.55 (m, 2H), 2.39–2.32 ppm (m, 2H); 13C NMR (100 MHz, CDCl3): d =
160.0, 148.4, 145.2, 137.8, 128.9, 128.3, 126.6, 113.7, 107.5, 57.9, 53.6, 49.6,
45.7, 33.2 ppm; GC-MS (EI, 70 eV): m/z: 357 [M +], 263, 238, 190, 165,
107, 71, 56, 42, 28; elemental analysis calcd (%) for C24H27N3: C 80.67, H
7.56, N 11.76; found: C 80.62, H 8.05, N 11.63.
N-(3,3-Diphenylpropyl)-4-pyrimid-2-yl-piperazine: Yield: 86%; 1H NMR
(400 MHz, CDCl3): d = 6.38–6.35 (m, 1H), 8.21–8.19 (m, 2H), 7.22–7.06
(m, 10H), 3.93 (t, J=7.2 Hz, 1H), 3.74 (t, J=4.9 Hz, 4H), 2.39 (t, J=
4.9 Hz, 4H), 2.26–2.21 (m, 2H), 2.08–1.98 ppm (m, 2H); 13C NMR
(100 MHz, CDCl3): d = 162.0, 158.1, 145.1, 128.9, 128.2, 126.6, 110.2,
57.4, 53.6, 49.5, 44.1, 33.1 ppm; GC-MS (EI, 70 eV): m/z: 358 [M +], 250,
177, 148, 122, 70, 41; elemental analysis calcd (%) for C23H26N4: C 77.09,
H 7.26, N 15.61; found: C 77.12, H 7.22, N 15.40.
N-(3,3-Diphenylpropyl)-pyridin-4-yl-amine: Yield: 35%; 1H NMR
(400 MHz, CDCl3): d = 7.86 (d, J=6.1 Hz, 2H), 7.23–7.09 (m, 10H),
6.36 (d, J=6.1 Hz, 2H), 3.96 (t, J=7.8 Hz, 1H), 3.10–3.04 (m, 2H), 2.34–
2.28 (m, 2H), 1.18 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d = 155.0,
145.7, 144.2, 129.1, 128.3, 126.1, 107.8, 49.1, 35.0, 31.0 ppm; GC-MS (EI,
70 eV): m/z: 288 [M +], 260, 209, 193, 179, 165, 152, 116, 107, 95, 78, 65,
51, 39; HRMS: m/z: calcd for C20H20N2: 288.3957; found: 288.3968 [M +].
53.8 Hz), 140.5, 139.1, 136.1, 134.1, 130.6, 129.1, 96.5 (d, JRh,C =7.4 Hz),
68.4 (d, JRh,C =14.0 Hz), 33.4, 29.1, 21.3, 20.1, 18.5 ppm; MS (EI, 70 eV):
m/z: 618 (32) [M +], 580 (27), 474 (9), 434 (40), 400 (40), 373 (100), 333
(40), 299 (10); HRMS: m/z: calcd for C29H34N2Cl3Rh: 618.0837; found
618.083 [M +].
[Chloro]-[(1,2,5,6-h)-1,5-cyclooctadiene]-[1,3-dihydro-1,3-bis(2,4-diiso-
propylphenyl)-2H-imidazol-2-ylidene]-rhodium(i) (4): Yield: 90%;
1H NMR (400 MHz, 233 K, [D8]THF): d = 7.54–7.48 (m, 4H), 7.46–7.42
(m, 2H), 7.36–7.33 (m, 2H), 4.46 (s, 2H), 3.72 (quint, J=6.6 Hz, 2H),
3.25 (s, 2H), 2.43 (quint, J=6.7 Hz, 2H), 1.82–1.74 (m, 2H), 1.72–1.61
(m, 2H), 1.54–1.43 (m, 4H), 1.42 (d, J=6.5 Hz, 6H), 1.30 (d, J=6.7 Hz,
6H), 1.08 ppm (d, J=7.0 Hz, 12H); 13C NMR (100 MHz, 233 K,
[D8]THF): d = 186.4 (d, JRh,C =51.9 Hz), 148.5, 146.4, 137.5, 130.4, 126.2,
125.2, 95.4 (d, JRh,C =7.4 Hz), 67.9 (d, JRh,C =25.8 Hz), 33.5, 29.9, 29.4,
29.1, 28.6, 23.9, 22.6 ppm; MS (EI, 70 eV): m/z: 634 (39) [M +], 490 (26),
429 (8), 389 (100), 355 (8), 281 (6), 186 (13), 149 (16). HRMS: m/z: calcd
for C35H48N2ClRh: 634.2556; found 634.254 [M +].
AHCTREUNG
=
7.40–7.30 (m, 2H), 4.45 (m, 2H), 3.78 (septet, J=6.6 Hz, 2H), 3.25 (m,
2H), 2.24 (m, 2H), 1.95 (s, 6H), 1.73 (m, 2H), 1.57 (m, 2H), 1.46 (m,
4H), 1.45 (d, J=6.3 Hz, 6H), 1.23 (d, J=6.6 Hz, 6H), 1.15 (d, J=6.8 Hz,
6H), 1.01 ppm (d, J=6.6 Hz, 6H); 13C NMR (100 MHz, 232 K,
[D8]THF): d
= 186.6 (d, JRh,C =50.4 Hz), 149.5, 147.0, 135.6, 130.7),
129.1, 126.4, 124.4, 94.8 (d, JRh,C =8.0 Hz), 68.0 (d, JRh,C =20.0 Hz), 33.7,
29.5, 29.3, 29.2, 27.1, 26.5, 25.6, 24.2, 10.9 ppm; MS (EI, 70 eV): m/z: 662
(45) [M +], 518 (100), 417 (84), 343 (9), 265 (20), 218 (26), 149 (20);
HRMS: m/z: calcd for C37H52N2ClRh: 627.3180; found 627.3173.
X-ray crystallographic study of compound 2 and 4: Data were collected
with a STOE-IPDS-diffractometer using graphite-monochromated MoKa
radiation. The structure was solved by direct methods (SHELXS-86)[26]
and refined by full-matrix least-squares techniques against F2 (SHELXL-
93).[27] XP (Bruker AXS) was used for structure representation.
N-(3,3-Diphenylpropyl)diisopropylamine:
Yield:
88%;
1H NMR
(400 MHz, CDCl3): d = 7.29–7.13 (m, 10H), 3.95 (t, J=7.5 Hz, 1H),
3.02–2.90 (m, 2H), 2.37–2.30 (m, 2H), 2.23–2.11 (m, 2H), 0.98 ppm (d,
J=6.6 Hz, 12H); 13C NMR (100 MHz, CDCl3): d = 143.0, 129.3, 128.4,
126.3, 49.4, 45.6, 40.1, 38.3, 22.0 ppm; GC-MS (EI, 70 eV): m/z: 295 [M +
], 300, 238, 210, 194, 181, 165, 152, 134, 120, 105, 91, 77, 58, 42.
Compound 2: Space group P21/c, monoclinic, a=13.993(3), b=12.057(2),
c=17.040(3) ,
b=100.48(3)8,
V=2826.9(9) 3,
Z=4,
1calcd =
1.360 gcmÀ3, 8329 reflections measured, 4450 were independent of sym-
metry and 2844 were observed (I > 2s (I)), R1=0.043, wR2 (all data)=
0.098, 316 parameters.
Synthesis of Rh–carbene catalysts: A THF solution (10 mL) of substitut-
ed imidazole-2-ylidene (1.0 mmol) at room temperature was added
slowly to a solution of [{Rh(cod)Cl}2](0.5 mmol) in THF (20 mL). The
E
Compound 4: Space group P21/c, monoclinic, a=17.563(4), b=11.208(2),
clear solution was stirred for 2 h and the solvent was evaporated. The res-
idue was triturated with pentane. The yellow solid obtained was analyti-
cally pure. It can be recrystallized from CH2Cl2/pentane.
c=18.774(4) , b=114.74(3)8, V=3356.4(12) 3, Z=4, 1calcd
=
1.312 gcmÀ3, 8073 reflections measured, 4387 were independent of sym-
metry and 3750 were observed (I > 2s(I)), R1=0.031, wR2 (all data)=
0.081, 370 parameters.
ACHTREUNG
1H NMR (400 MHz, 297 K, CDCl3): d = 7.03 (s, 4H), 6.96 (s, 2H), 4.40
(s, 2H), 3.30 (s, 2H), 2.38 (s, 6H), 2.34 (s, 6H), 2.10 (s, 6H), 1.83 (m,
4H), 1.54 ppm (m, 4H); 13C NMR (100 MHz, 297 K, CDCl3): d = 183.5
(d, 1JRh,C =52.5 Hz), 139.2, 137.9, 137.0, 135.1, 129.8, 128.8, 124.3, 96.3 (d
1JRh,C =7.6 Hz), 68.7 (d, 1JRh,C =14.3 Hz), 33.2, 28.9, 21.4, 20.0, 18.5 ppm;
MS (EI, 70 eV): m/z: 550 (13) [M +], 404 (21), 303 (100); elemental anal-
ysis calcd (%) for C29H36CIN2Rh (550.98): C 63.22, H 6.58, N 5.08;
found: C 63.08, H 6.34, N 5.05.
Acknowledgements
This work has been financed by the State of Mecklenburg-Pomerania
and the Bundesministerium für Bildung und Forschung (BMBF). Addi-
tional support came from the DFG (“Leibniz-Preis”). We thank Mrs. I.
Stahr, Mrs. C. Mewes, Mrs. S. Buchholz, Dr. C. Fischer and Dr. W. Bau-
mann (all Leibniz-Institut für Katalyse e.V.) for their excellent technical
and analytical support.
A
thylphenyl)-4,5-dimethyl-2H-imidazol-2-ylidene]-rhodium(i) (2): Yield:
1
90%; H NMR (400 MHz, 297 K, [D8]THF): d = 7.04–7.03 (m, 4H), 4.40
(m, 2H), 3.31 (m, 2H), 2.37 (s, 12H), 1.99 (s, 6H), 1.80 (s, 6H), 1.75–1.70
(m, 4H), 1.63–1.34 ppm (m, 4H); 13C NMR (75 MHz, 297 K, [D8]THF):
d = 182.8 (d, JRh,C =52 Hz), 139.3, 139.2, 136.0, 130.6, 129.0, 127.4, 95.4
(d, JRh,C =7.7 Hz), 67.3 (d, JRh,C =14.1 Hz), 33.7, 29.3, 21.4, 20.5, 18.6,
9.2 ppm; MS (EI, 70 eV): m/z: 578 (39) [M +], 542 (7), 434 (40), 333
(100); HRMS: m/z: calcd for C31H40N2ClRh: 578.1930; found 578.1920
[M +].
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Kitsos-Rzychon, C. L. Kranemann, T. Rische, R. Roggenbuck, A.
Schmidt, Chem. Rev. 1999, 99, 3329–3365; b) F. Ungvary, Coord.
Chem. Rev. 2004, 248, 867–880.
A
[2]a) L. Routaboul, C. Buch, H. Klein, R. Jackstell, M. Beller, Tetrahe-
dron Lett. 2005, 46, 7401–7405; b) I. D. Kostas, J. Chem. Res. Synop.
1600
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 1594 – 1601