K. Verlinden, C. Ganter / Journal of Organometallic Chemistry 750 (2014) 23e29
27
(s, naphthyl), 97.00 (s, Cp*), 88.48 (s, naphthyl), 84.80 (s, naphthyl),
84.27 (s, naphthyl), 76.40 (s, naphthyl), 40.90 (s, methyl), 40.75 (s,
methyl), 9.57 (s, MeeCp*); MS (MALDI-TOF): m/z: 197 [M ꢀ RuCp*]þ,
433 [M]þ elemental analyses calcd (%) for [C23H28N2Ru][PF6]2$1/
3THF: C 39.42, H 4.11, N 3.73; found C 39.46, H 4.46, N 3.65.
4.3.4. Alternative synthesis of complex 8
71 mg (0.13 mmol) of compound 11 and 76 mg (0.15 mmol)
[Cp*Ru(MeCN)3]PF6 were dissolved in 10 ml CH2Cl2 and stirred for
24 h at ambient temperature. The brown solution was concentrated
in vacuo and addition of 15 ml Et2O caused precipitation of a yellow
solid. After decanting of the solvent the product was washed with
Et2O and dried in vacuo. Purification by column chromatography
(alumina/CH2Cl2: acetone (1:1)) afforded a pure product in 89%
yield (105 mg 0.12 mmol).
4.3. General procedure for the synthesis of codemetal complexes
0.80 mmol of the NHC-precursor, 1.00 mmol KOtBu and
0.40 mmol [M(cod)Cl]2 (M ¼ Rh or Ir) were dissolved in 20 ml THF
at ꢀ78 ꢁC. After stirring for 20 min at low temperature the mixture
was allowed to warm to room temperature while stirring was
continued for another 24 h. The solvent was removed in vacuo and
the product can be further purified by column chromatography on
alumina.
4.3.5. Chloro(h
4-1,5-cyclooctadiene)(1,3-dimethylperimidin-2-
ylidene)rhodium(I) (10)
Yield: 72% (0.58 mmol) yellow powder. 1H NMR (CDCl3):
d/
ppm ¼ 7.33 (m, 4H, naphthyl), 6.64 (m, 2H, naphthyl), 5.06 (m, 2H,
cod), 4.52 (s, 6H, methyl), 3.38 (m, 2H, cod), 2.44 (m, 4H, cod), 1.95
(m, 4H, cod); 13C{1H} NMR (CDCl3):
d
/ppm ¼ 211.78 (d, JRhe
1
4.3.1. Chloro(
pentamethylcyclopentadienyl)(
h
4-1,5-cyclooctadiene){(h5
-
¼ 49 Hz, carbeneeC), 135.11 (s, naphthyl), 134.34 (s, naphthyl),
C
h
6-1,3-dimethylperimidin-2-ylidene)
127.93 (s, naphthyl), 121.22 (s, naphthyl), 119.86 (s, naphthyl), 104.53
1
1
ruthenium(II)}rhodium(I) hexafluorophosphate (7)
(s, naphthyl), 98.38 (d, JRheC ¼ 7 Hz, cod-olefin), 70.25 (d, JRhe
Yield: 64% (0.51 mmol). 1H NMR (acetone-d6):
d
/ppm ¼ 7.79
¼ 17 Hz, cod-olefin), 43.35 (s, methyl), 32.71 (s, cod-aliph), 29.04 (s,
C
(dd, J ¼ 7.6, 8.8, 1H, naphthyl), 7.28 (d, J ¼ 8.7, 1H, naphthyl), 7.17
(d, J ¼ 7.5, 1H, naphthyl), 6.53 (d, J ¼ 6.1, 1H, naphthyl), 6.29 (t,
J ¼ 6.1, 1H, naphthyl), 5.01 (m, 2H, cod), 4.75 (s, 3H, methyl), 4.69
(s, 3H, methyl), 3.60 (m, 2H, cod), 2.48 (m, 4H, cod), 2.00 (m, 4H,
cod-aliph); MS (MALDI-TOF): m/z: 442 [M]þ, 407 [M ꢀ Cl]þ;
elemental analysis calcd (%) for C21H24N2RhCl: C 56.96, H 5.46, N
6.33; found C 56.77, H 5.41, N 6.13.
cod), 1.73 (s, 15H, Cp*); 13C{1H} NMR (acetone-d6):
d
/
4.3.6. Chloro(h
4-1,5-cyclooctadiene)(1,3-dimethylperimidin-2-
ppm ¼ 214.70 (s, carbeneeC), 135.68 (s, naphthyl), 133.36 (s,
ylidene)iridium(I) (11)
naphthyl), 120.55 (s, naphthyl), 108.32 (s, naphthyl), 99.37 (d, 1JRhe
Yield: 77% (0.62 mmol) yellow powder. 1H NMR (CDCl3):
d/
¼ 7 Hz, cod-olefin), 98.42 (s, naphthyl), 97.58 (s, naphthyl), 95.15
ppm ¼ 7.33 (m, 4H, naphthyl), 6.64 (m, 2H, naphthyl), 4.66 (m, 2H,
C
(s, Cp*), 87.71 (s, naphthyl), 83.70 (s, naphthyl), 83.24 (s, naph-
cod), 4.30 (s, 6H, methyl), 3.01 (m, 2H, cod), 2.26 (m, 4H, cod), 1.70
1
thyl), 73.58 (s, naphthyl), 71.74 (d, JRheC ¼ 11 Hz, cod-olefin),
(m, 4H, cod); 13C{1H} NMR (CDCl3):
d/ppm ¼ 204.38 (s, carbeneeC),
1
71.63 (d, JRheC ¼ 11 Hz, cod-olefin) 44.48 (s, methyl), 33.04 (s,
136.19 (s, naphthyl), 134.59 (s, naphthyl), 128.20 (s, naphthyl), 121.32
(s, naphthyl), 119.93 (s, naphthyl), 104.86 (s, naphthyl), 84.58 (s, cod-
olefin), 54.25 (s, cod-olefin), 43.01 (s, methyl), 33.56 (s, cod-aliph),
29.74 (s, cod-aliph); MS (MALDI-TOF): m/z: 532 [M]þ; elemental
analysis calcd (%) for C21H24N2IrCl: C 47.40, H 4.55, N 5.26; found C
47.63, H 4.46, N 5.22.
1JRheC ¼ 5 Hz, cod-aliph), 9.57 (s, MeeCp*); MS (MALDI-TOF): m/
z: 679 [M]þ, 433 [M ꢀ Rh(cod)Cl]þ; elemental analysis calcd (%)
for [C31H39N2ClRhRu][PF6]: C 45.18, H 4.77, N 3.40; found C 46.08;
H 5.26, N 3.13.
4.3.2. Alternative synthesis of complex (7)
105 mg (0.24 mmol) of compound 10 and 131 mg (0.26 mmol)
[Cp*Ru(MeCN)3]PF6 were dissolved in 30 ml CH2Cl2 and stirred for
24 h at ambient temperature. The brown solution was concentrated
in vacuo and addition of 25 ml Et2O caused precipitation of a yellow
solid. After decanting of the solvent the product was washed with
Et2O and dried in vacuo. Purification by column chromatograph
(alumina/CH2Cl2:acetone (1:1)) afforded a pure product in 93%
yield (184 mg 0.22 mmol).
4.4. General procedure for the synthesis of dicarbonyl complexes
The cod-complex was dissolved in CH2Cl2 and a stream of CO-
gas was bubbled through the solution under stirring for 30 min.
The decoloration of the yellow starting solution indicated a
complete conversion. IR spectra of the resulting dicarbonyle
NHC-compounds were recorded from the reaction solution. For
recording of the NMR-spectra the CO-complexes were dissolved
4.3.3. Chloro(
h
4-1,5-cyclooctadiene){(h5
-
in a suitable deuterated solvent after evaporation of the
dichloromethane.
pentamethylcyclopentadienyl)(
h
6-1,3-dimethylperimidin-2-ylidene)
ruthenium(II)}iridium(I) hexafluorophosphate (8)
Yield: 72% (105 mg, 0.58 mmol). 1H NMR (acetone-d6):
d
/
4.4.1. Chloro(dicarbonyl){(h -
5-pentamethylcyclopentadienyl)(h6
ppm ¼ 7.79 (dd, J ¼ 7.5, 8.8, 1H, naphthyl), 7.34 (d, J ¼ 8.9, 1H,
naphthyl), 7.22 (d, J ¼ 7.6, 1H, naphthyl), 6.57 (m, 2H, naphthyl),
6.32 (m, 1H, naphthyl), 4.66 (m, 2H, cod), 4.57 (s, 3H, methyl), 4.51
(s, 3H, methyl), 3.26 (m, 2H, cod), 2.32 (m, 4H, cod), 1.82 (m, 4H,
1,3-dimethylperimidin-2-ylidene)ruthenium(II)}rhodium(I)
hexafluorophosphate (12)
Yield: 73% (from NMR spectrum). 1H NMR (acetone-d6):
d/
ppm ¼ 7.85 (m, 1H, naphthyl), 7.41 (d, J ¼ 8.8, 1H, naphthyl), 7.32
(d, J ¼ 7.5, 1H, naphthyl), 6.64 (m, 2H, naphthyl), 6.39 (m, 1H,
naphthyl), 5.52 (m, free cod), 4.34 (s, 3H, methyl), 4.28 (s, 3H,
cod), 1.77 (s, 15H, Cp*); 13C{1H} NMR (acetone-d6):
d/
ppm ¼ 207.23 (s, carbeneeC), 134.61 (s, naphthyl), 131.52 (s,
naphthyl), 118.39 (s, naphthyl), 106.59 (s, naphthyl), 104.18 (s,
naphthyl), 96.47 (s, naphthyl), 93.34 (s, Cp*), 85.51 (s, naphthyl),
84.78 (s, cod-olefin), 84.58 (s, cod-olefin), 81.54 (s, naphthyl),
81.10 (s, naphthyl), 71.32 (s, naphthyl), 54.38 (s, cod-olefin), 54.24
(s, cod-olefin), 41.72 (s, methyl), 31.76 (s, cod-aliph), 31.47 (s, cod-
aliph), 28.00 (s, cod-aliph), 27.73 (s, cod-aliph), 7.32 (s, MeeCp*);
MS (MALDI-TOF): m/z: 769 [M]þ; elemental analyses calcd (%) for
[C31H39N2ClIrRu][PF6]: C 40.77, H 4.30, N 3.07; found C 36.70, H
4.33, N 2.51.
methyl), 2.34 (m, free cod) 1.77 (s, 15H, Cp*); 13C{1H} NMR
1
(acetone-d6):
d
/ppm ¼ 210.47 (s, carbeneeC), 187.70 (d, JRhe
¼ 55 Hz, CO), 182.85 (d, 1JRheC ¼ 75 Hz, CO), 135.69 (s, naphthyl),
C
133.58 (s, naphthyl), 129,67 (s, free cod), 122.44 (s, naphthyl),
110.58 (s, naphthyl), 98.49 (s, naphthyl), 96.02 (s, Cp*), 95.74 (s,
naphthyl), 88.23 (s, naphthyl), 84.647 (s, naphthyl), 84,07 (s,
naphthyl), 74.87 (s, naphthyl), 45.48 (s, methyl), 45.42 (s, methyl),
ꢀ1
~
29.02 (s, free cod), 9.95 (s, MeeCp*); IR (CH2Cl2): v/cm ¼ 2013,
2092.