M. Igarashi et al. / Journal of Organometallic Chemistry 752 (2014) 141e146
145
(15.5 mg, 0.101 mmol) in a 0.5 mL sealed tube were added
chloro(1,5-cyclooctadiene)iridium(I) dimer (1.70 mg, 2.53 mol)
chloro(1,5-cyclooctadiene)iridium(I) dimer (1.70 mg, 2.53
m
mol)
m
under argon. The reaction mixture was gradually heated to 40 ꢀC
under argon. The reaction mixture was gradually heated
and stirred for 3 h giving a hydrosilylation product, T1R10.98R02.02
T1R01.98R02.02 1H NMR (CDCl3):
.
to 40 ꢀC and stirred for 3 h giving a hydrosilylation product,
:
d
(ppm) ¼ 0.53e0.70 (m, 2.0 H,
MM0R10.55R02.09R30.03R50.18
.
SiCH2CH2CH2), 1.15e1.29 (m, 9.0 H, SiOCH2CH3), 1.67e1.78 (m, 2.0
H, SiCH2CH2CH2), 1.94e2.06 (m, 3.0 H, (C]O)CH3), 3.72e3.89
(m, 6.0 H, SiOCH2CH3), 3.96e4.06 (m, 2.0 H, CH2CH2CH2O); 13C
MM0R10.55R02.09R30.03R50.18
:
1H NMR (CDCl3):
d
(ppm) ¼ 0.06e0.34
(m, 15.0 H, Si(CH3)2, Si(CH3)3), 0.52e0.72 (m, 1.2 H, SiCH2CH2CH2,
SiCH2CH2CH3), 0.93e1.06 (m, 0.1 H, SiCH2CH2CH3), 1.38e1.47 (m,
0.1 H, SiCH2CH2CH3), 1.60e1.79 (m, 1.1 H, SiCH2CH2CH2), 2.02e2.10
(m, 1.9 H, (C]O)CH3), 4.03e4.12 (m, 1.1 H, CH2CH2CH2O), 4.73e4.79
NMR (CDCl3):
((C]O)CH3), 22.0 (SiCH2CH2CH2), 58.1 (SiOCH2CH3), 66.2
(CH2CH2CH2O), 170.6 (C]O); 29Si NMR (CDCl3):
(ppm) ¼ ꢁ46.1
(SiCH2CH2CH2), (SiO(C]O)CH3 was not observed).
d
(ppm) ¼ 6.3 (SiCH2CH2CH2), 18.0 (SiOCH2CH3), 20.5
d
(m, 0.2 H, SiH); 13C NMR (CDCl3):
Si(CH3)3), 14.1 (SiCH2CH2CH2), 16.7 (SiCH2CH2CH3), 18.0 (SiCH2
CH2CH3), 20.6e20.8 ((C]O)CH3), 21.9 (SiCH2CH2CH3), 22.6
(SiCH2CH2CH2), 66.8 (CH2CH2CH2O), 170.6e170.8 (C]O); 29Si NMR
d
(ppm) ¼ ꢁ2.9 to 2.0 (m, Si(CH3)2,
4.9. Experimental procedure of the hydrosilylation of AA with T01H1
and spectral data of the product (Table 2, entry 5)
(CDCl3):
d
(ppm) ¼ e16.3, e9.1, e6.9 (SiH), 7.3 (SiCH2CH2CH2), 7.6
(Si(CH3)3), 9.3, 9.6(Si(CH3)3), 10.2.
To a stirred mixture of dehydrated toluene-d8 (50.0
mL), AA
(111 mg 1.09 mmol), T01H1 (297 mg, 0.982 mmol) and biphenyl
(15.6 mg, 0.101 mmol) in a 0.5 mL sealed tube were added
4.6. Experimental procedure of the hydrosilylation of AA with M2H2
and spectral data of the product (Table 2, entry 2)
chloro(1,5-cyclooctadiene)iridium(I) dimer (1.70 mg, 2.53
mmol)
under argon. The reaction mixture was gradually heated to
To a stirred mixture of dehydrated toluene-d8 (50.0
(111 mg 1.08 mmol), M2H2 (67.4 mg, 0.492 mmol) and biphenyl
(15.7 mg, 0.101 mmol) in a 0.5 mL sealed tube were added
mL), AA
40 ꢀC and stirred for 3 h giving a hydrosilylation product,
T01R10.33R20.02R30.01R40.02R05.58
.
T01R10.33R20.02R30.01R50.58: 1H NMR (CDCl3):
d
(ppm) ¼ 0.01e0.27 (m,
chloro(1,5-cyclooctadiene)iridium(I) dimer (1.70 mg, 2.53
mmol)
27.0 H, OSi(CH3)3), 0.45e0.62 (m, 0.7 H, SiCH2CH2CH2,
SiCH2CH2CH3), 0.91e0.99 (m, 0.03 H, SiCH2CH2CH3), 1.47e1.54 (m,
0.02 H, SiCH2CH2CH3), 1.57e1.77 (m, 0.7 H, SiCH2CH2CH2,
SiCH2CH]CH2), 1.98e2.14 (m, 1.1 H, (C]O)CH3), 3.96e4.11 (m, 0.7
H, CH2CH2CH2O), 4.26e4.31 (m, 0.6 H, SiH), 4.91e5.07 (m, 0.04 H,
SiCH2CH]CH2), 5.76e5.85 (m, 0.02 H, SiCH2CH]CH2); 13C NMR
under argon. The reaction mixture was gradually heated to
40 ꢀC and stirred for 3 h giving a hydrosilylation product,
M2R11.14R20.25R30.03R05.55
.
M2R11.14R02.25R30.03R05.55: 1H NMR (CDCl3):
d
(ppm) ¼ 0.07e0.40 (m,
12.0 H, Si(CH3)2), 0.52e0.72 (m, 2.3 H, SiCH2CH2CH2, SiCH2CH2CH3),
0.93e1.04 (m, 0.1 H, SiCH2CH2CH3), 1.37e1.47 (m, 0.1 H,
SiCH2CH2CH3), 1.58e1.78 (m, 2.3 H, SiCH2CH2CH2), 2.02e2.10 (m,
4.2 H, (C]O)CH3), 4.02e4.10 (m, 2.3 H, CH2CH2CH2O), 4.72e4.81
(CDCl3):
d
(ppm) ¼ 0.9e2.0 (m, OSi(CH3)3),10.3 (SiCH2CH2CH2), 16.3
(SiCH2CH2CH3), 19.2 (SiCH2CH]CH2), 20.4 (SiCH2CH2CH3), 20.7e
20.8 ((C]O)CH3), 21.9 (SiCH2CH2CH3), 22.7 (SiCH2CH2CH2), 66.6
(CH2CH2CH2O), 115.5 (SiCH2CH]CH2), 133.4 (SiCH2CH]CH2),
(m, 0.6 H, SiH); 13C NMR (CDCl3):
d
(ppm) ¼ ꢁ2.9 to 1.4
(m, Si(CH3)2), 13.6e14.1 (m, SiCH2CH2CH2), 16.6 (SiCH2CH2CH3),
17.9 (SiCH2CH2CH3), 20.5e20.9 ((C]O)CH3), 21.8 (SiCH2CH2CH3),
22.2e22.6 (m, SiCH2CH2CH2), 66.5e66.8 (m, CH2CH2CH2O), 170.6e
170.7e170.9 (C]O); 29Si NMR (CDCl3):
d
(ppm) ¼ ꢁ104.5 (SiO(C]
O)CH3), e82.8 (SiH), e66.3 (SiCH2CH2CH2), 7.7 (OSi(CH3)3), 9.3
(OSi(CH3)3), 11.1 (OSi(CH3)3), (SiCH2CH2CH3 and SiCH2CH=CH2
were not observed).
170.9 (C]O); 29Si NMR (CDCl3):
e7.5, e6.4 (SiH), e4.1 (SiH), 4.8, 7.1, 7.8 (SiCH2CH2CH2), 9.6
(SiCH2CH2CH2), 10.3, 12.7.
d
(ppm) ¼ ꢁ16.3, e9.3, e9.0, e7.6,
References
4.7. Experimental procedure of the hydrosilylation of AA with T8H8
and spectral data of the product (Table 2, entry 3)
To a stirred mixture of dehydrated toluene-d8 (50.0
(109 mg 1.06 mmol), T8H8 (53.9 mg, 0.127 mmol) and biphenyl
(15.3 mg, 0.099 mmol) in a 0.5 mL sealed tube were added
mL), AA
chloro(1,5-cyclooctadiene)iridium(I) dimer (1.70 mg, 2.53
under argon. The reaction mixture was gradually heated to 40 ꢀC and
stirred for 3 h giving a hydrosilylation product, T8R12.47R20.09R30.02R45.67
T8R12.47R02.09R03.02R45.67: 1H NMR (CDCl3):
mmol)
.
d
(ppm) ¼ 0.62e0.87 (m,
5.0 H, SiCH2CH2CH2, SiCH2CH2CH3), 0.97e1.01 (m, 0.1 H,
SiCH2CH2CH3), 1.30e1.34 (m, 0.04 H, SiCH2CH2CH3), 1.74e1.88 (m,
4.9 H, SiCH2CH2CH2), 2.03e2.21 (m, 7.7 H, (C]O)CH3), 4.03e4.16
(m, 4.9 H, CH2CH2CH2O), 4.20e4.32 (m, 4.7 H, SiH); 13C NMR
(CDCl3):
21.7e22.2 (m, SiCH2CH2CH2), 65.8e66.1 (m, CH2CH2CH2O), 170.8e
171.0 (C]O); 29Si NMR (CDCl3):
d
(ppm) ¼ 7.6e8.0 (m, SiCH2CH2CH2), 20.8 ((C]O)CH3),
d
(ppm) ¼ e84.7 to e84.2 (m, SiH),
e66.8 to e66.6 (m, SiCH2CH2CH2), (SiO(C]O)CH3 and SiCH2CH2CH3
were not observed).
4.8. Experimental procedure of the hydrosilylation of AA with T1H1
and spectral data of the product (Table 2, entry 4)
To a stirred mixture of dehydrated toluene-d8 (50.0
(111 mg 1.09 mmol), T1H1 (168 mg, 1.00 mmol) and biphenyl
(16.2 mg, 0.105 mmol) in a 0.5 mL sealed tube were added
mL), AA