A. A. Danopoulos, D. J. Cole-Hamilton et al.
FULL PAPER
J = 7 Hz, 3 H, CH(CH3)2], 0.86 [d, J = 7 Hz, 3 H, CH(CH3)2]
bridge), 3.60–3.26 [m, 10 H, COD and CH(CH3)2], 3.20 (s, 3 H,
ppm. 13C{1H} NMR: δ = (C6D6, 75 MHz): 146.9 (Ar), 144.4 (Ar), indenyl-methyl), 2.90–2.75 (m, 2 H, broad bridge), 2.60 (s, 3 H,
142.5 (Ar), 141.3 (Ar), 140.7 (Ar), 134.8 (Ar), 129.7 (ArH), 128.7
(Ar), 128.6 (ArH), 127.1 (ArH), 125.2 (ArH), 123.8 (ArH), 123.6
indene-methyl), 1.95–1.65 (m, 8 H, COD), 1.60–1.20 (m, 4 H,
COD), 1.40 [d, 3 H, CH(CH3)2], 1.00 [d, 3 H, CH(CH3)2], 0.95 [d,
(ArH), 122.1 (ArH), 119.3 (ArH), 95.6 (CH), 95.5 (CH), 95.4 (CH), J = 7 Hz, 3 H, CH(CH3)2], 0.85 [d, J = 7 Hz, 3 H, CH(CH3)2]
68.0 (CH2), 67.6 (CH2), 66.9 (CH2), 50.9 (CH2), 35.4 (CH2), 32.3
(CH2), 30.7 (CH2), 30.4; (CH2), 28.1 (CH), 27.7 (CH), 27.4 (CH),
27.3 (CH), 27.2 (CH), 24.8 (CH2), 24.6 (CH), 23.2 (CH), 22.9 (CH),
27.8 (CH), 19.1 (CH), 17.3 (CH) ppm. C36H46BrN2Rh (689.58):
calcd. C 62.61, H 6.86, N 4.06; found C 62.60, H 6.59, N 3.95.
ppm.
Crystal data: CCDC-710642 (for 4b), empirical formula
C44H57BrN2Rh2, formula weight 899.65, crystal system mono-
clinic, space group P21/n, a = 15.539(3) Å, b = 26.596(5) Å, c =
20.236(4) Å, α = 90°, β = 111.73(3)°, γ = 90°, V = 7769(3) Å3, Z
= 8, T = 120(2) K, µ = 1.911 mm–1, data collected 63459, unique
Crystal data: CCDC-710640 (for 3b), empirical formula
C36H46BrN2Rh, formula weight 689.58, crystal system triclinic, data 16317, goodness of fit on F2 = 1.029, Rint. = 0.0699, final
space group P1, a = 8.2436(2) Å b = 8.5687(3) Å c = 22.8614(8) Å,
R(|F|) for Fo Ͼ 2σ(Fo) = 0.0514, final R(F2) for all data 0.1470.
¯
α = 81.819(2)° β = 85.004(2)° γ = 82.286(2)° V = 1580.15(9) Å3 Z
= 2, T = 120(2) µ = 1.832, data collected 32381, unique data 7288,
goodness of fit on F2 = 1.171, Rint. = 0.0647, final R(|F|) for Fo Ͼ
2σ(Fo) = 0.0955, final R(F2) for all data 0.2427.
Formation of Complex 5: [Rh(COD)(Cl)]2 (0.25 mmol, 120 mg) and
the (Flu-NHC)–K+ (0.5 mmol, 230 mg) were combined as solids
and precooled (–78 °C) THF (20 mL) was added at –78 °C. The
mixture was allowed to reach room temperature slowly (ca. 2 h)
and the solution was concentrated, filtered and layered with ether
to give yellow crystals of 5 in low yield (ca. 20 mg). Analytically
pure samples could not be obtained due to contamination with
other rhodium-containing unidentifiable products.
Synthesis of Complex 3c: IndHMe-NHC-AgBr (1.0 mmol, 560 mg)
and [Rh(COD)Cl]2 (0.5 mmol, 250 mg) were dissolved in toluene
(10 mL) and heated to reflux for 18 h, the resulting solution was
filtered through Celite and the solvents evaporated to dryness to
give the crude product. Crystallization took place from toluene
(10 mL) layered with petroleum ether (50%, 310 mg). 1H NMR
(C6D6, 400 MHz): δ = 7.48 (d, J = 8 Hz, 1 H, Ar), 7.36 (t, J =
8 Hz, 1 H, Ar), 7.27 (dd, Ar, J = 8.2 Hz, 1 H), 7.24 (t, J = 8 Hz, 1
H, Ar), 7.18–7.10 (m, 2 H, Ar), 7.07 (dd, J = 8.2 Hz, 1 H, Ar),
6.87 (d, J = 2 Hz, 1 H, NCH), 6.67 (d, J = 2 Hz, 1 H, NCH), 6.12
(s, 1 H, indene-H), 5.54–5.47 (m, 1 H, indene-H), 4.77–4.72 (m, 1
H, indene-H), 4.68–4.64 (m, 1 H, bridge), 4.53–4.46 (m, 1 H,
bridge), 3.40 [sept, J = 7 Hz, 1 H, CH(CH3)2], 3.23 [sept, J = 7 Hz,
1 H, CH(CH3)2], 3.10–3.06 (m, 1 H, bridge), 2.74–2.72 (m, 1 H,
bridge), 2.01–1.96 (m, 4 H, COD-CH ϫ4), 1.61–1.38 (m, 5 H,
COD-CH2 ϫ5), 1.36–1.28 (m, 3 H, COD-CH2 ϫ3), 1.42 [d, J =
7 Hz, 3 H, CH(CH3)2], 1.00 [d, J = 7 Hz, 3 H, CH(CH3)2], 0.98 [d,
J = 7 Hz, 3 H, CH(CH3)2], 0.86 [d, J = 7 Hz, 3 H, CH(CH3)2]
ppm. 13C{1H} NMR (C6D6, 100 MHz): δ = 146.9 (Ar), 144.3 (Ar),
143.7 (Ar), 143.2 (Ar), 129.2 (ArH), 128.7 (ArH), 125.3 (Ar), 123.9
(ArH), 123.5 (ArH), 122.9 (ArH), 121.9 (ArH), 119.3 (ArH), 118.0
(ArH), 95.9 (indene-CH), 66.9 (COD), 66.8 (indene-C), 66.7 (CH2),
49.8 (CH2), 36.9 (CH2), 32.6 (CH2), 30.6 (CH2), 30.5 (CH), 29.9
(CH2), 28.3 (CH2), 27.8 (CH), 27.3 (CH), 27.1 (CH2), 27.0
[CH(CH3)2], 25.4 [CH(CH3)2], 24.9 [CH(CH3)2], 22.6 [CH(CH3)2]
ppm. MS (ES+): m/z = 581 [M – Br–]. Accurate MS (ES+): Calcu-
lated 581.2385; found 581.2385. C34H42BrN2Rh: calcd. C 66.18, H
6.86, N 4.54; found C 66.12 H, 6.91, N 4.56.
Crystal data: CCDC-710643 (for 5), empirical formula
C38H43N2Rh, formula weight 630.65, crystal system triclinic, space
group P1, a = 9.5366(5) Å, b = 10.3587(5) Å, c = 17.5823(9) Å, α
¯
= 82.455(2)°, β = 88.949(2)°, γ = 63.153(2)°, V = 1534.62(13) Å3,
Z = 2, T = 120(2) K, µ = 0.586 mm–1, data collected 46366, unique
data 7053, goodness of fit on F2 = 1.028, Rint. = 0.0683, final R(|F|)
for Fo Ͼ 2σ(Fo) = 0.0392, final R(F2) for all data 0.0833.
Synthesis of Complex 6: [Rh(CO)2Cl]2 (0.5 mmol, 190 mg) and
(IndMe-NHC)–K+ (1.0 mmol, 440 mg) were dissolved in THF
(20 mL) and cooled to –78 °C. The two solutions were combined.
The reaction mixture was warmed to room temperature and stirred
overnight. The volatiles were removed under reduced pressure. The
residue was dissolved in toluene (10 mL) and filtered through Ce-
lite. The toluene solution was layered with diethyl ether. X-ray-
quality crystals formed and were isolated by filtration (80%,
1
424 mg). H NMR (C6D6, 400 MHz): δ = 7.41 (m, 4 H, Ar), 7.08
(d, J = 7 Hz, 1 H, Ar), 6.81–6.74 (m, 1 H, Ar), 6.49 (d, J = 2 Hz,
1 H, NCH), 6.28 (d, J = 2 Hz, 1 H, NCH), 4.92–4.80 (m, 1 H,
bridge), 3.60–3.50 (m, 1 H, bridge), 3.50–3.40 (m, 1 H, bridge),
3.20–3.12 (m, 1 H, bridge), 2.50 (s, 3 H, indene-CH3), 2.25 (s, 3 H,
indene-CH3), 2.32–2.18 [m, 2 H, CH(CH3)2], 1.44 [d, J = 7 Hz, 6
H, CH(CH3)2], 1.09 [d, J = 7 Hz, 6 H, CH(CH3)2] ppm. 13C{1H}
NMR (C6D6, 100 MHz): δ = 145.6 (Ar), 141.8 (Ar), 129.1 (Ar),
128.7 (Ar), 128.1 (ArH), 127.3 (ArH), 124.8 (ArH), 124.4 (Ar),
122.3 (Ar), 122.0 (Ar), 118.9 (ArH), 57.3 (CH2), 49.4 (CH2), 35.2
(indenyl-CH3), 30.4 (indenyl-CH3), 28.0 [CH(CH3)2], 27.1
[CH(CH3)2], 25.2 [CH(CH3)2], 21.7 [CH(CH3)2], 18.7 [CH(CH3)2],
16.9 [CH(CH3)2] ppm. C29H33N2ORh: calcd. C 65.91, H 6.29, N
Crystal data: CCDC-710641 (for 3c), empirical formula
C34H42BrN2Rh, formula weight 661.52, crystal system orthorhom-
bic, space group P212121, a = 11.795(4) Å, b = 11.853(3) Å, c =
21.599(5) Å, α = 90°, β = 90°, γ = 90°, V = 3019.7(15) Å3, Z = 4,
T = 120(2) K, µ = 1.914 mm–1, data collected 17562, unique data
6733, goodness of fit on F2 = 0.973, Rint. = 0.1500, final R(|F|) for
Fo Ͼ 2σ(Fo) 0.0783, final R(F2) for all data 0.1520.
5.31; found C 65.41, H, 6.32, 5.41. IR (film from toluene): ν =
2966, 2918, 2860, 1927 (s), 1464.
˜
Crystal data: CCDC-710644 (for 6), empirical formula
Synthesis of Complex 4b: Complex 3b (0.5 mmol) and [Rh(CO-
D)(OMe)]2 (0.25 mmol) were dissolved in toluene (20 mL) and
heated to reflux overnight. After cooling the toluene was removed
under vacuum and the residues dissolved in THF (10 mL). After
C29H33N2ORh, formula weight 528.48, crystal system triclinic,
¯
space group P1, a = 10.4658(7) Å, b = 11.8571(9) Å, c =
13.2432(8) Å, α = 103.269(3)°, β = 103.291(4)°, γ = 114.368(3)°, V
= 1355.87(16) Å, Z = 2, T = 120(2) K, µ = 0.651 mm–1, data col-
lected 26187, unique data 6244, goodness of fit on F2 = 1.043, Rint.
= 0.0546, final R(|F|) for Fo Ͼ 2σ(Fo) = 0.1241, final R(F2) for all
data 0.1286.
1
filtering the THF was layered with ether to give crystals of 4b. H
NMR ([D8]THF, 300 MHz): δ = 7.38 (d, 1 H, Ar), 7.25 (dd, J =
8.2 Hz, 1 H, Ar), 7.10 (dd, 1 H, Ar), 6.91 (d, J = 7 Hz, 1 H, Ar),
6.85 (d, J = 2 Hz, 1 H, NHC), 6.83 (d, J = 7 Hz, 1 H, Ar), 6.72
(d, 1 H, NHC), 5.65–5.50 (m broad, 2 H, bridge), 4.90–4.80 (m, 2
Synthesis of Complex 7: Salt (IndMe-NHC)K (0.5 mmol, 220 mg)
H, COD), 4.78–4.69 (m, 2 H, COD), 4.60–4.45 (m, 2 H, broad, and [Ir(COD)Cl]2 (0.25 mmol, 176 mg) was dissolved in THF
1822 Eur. J. Inorg. Chem. 2009, 1816–1824
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