10.1002/cctc.201900132
ChemCatChem
FULL PAPER
3
=2.4 Hz), 4.08 (m, 1H, CH2-S), 4.11 (b, 1H, CH=, cod), 4.44 (m, 1H, CH=,
cod), 4.49 (m, 2H, CH-O, CHCH2S), 4.86 (b, 1H, CH=, cod), 4.97 (b, 1H,
CH=, cod), 7.15-8.06 (m, 23H, CH= aromatic). 13C NMR (100.6 MHz,
CDCl3): δ=18.8 (CH3), 26.9 (CH3), 27.0 (CH3), 28.1 (d, CH2, cod, JC-P
=3.0 Hz), 29.9 (b, CH2, cod), 31.5 (CH3, Bu), 31.6 (CH3, Bu), 32.0 (d,
CH2, cod, JC-P =2.1 Hz), 32.2 (CH3, tBu), 33.8 (d, CH2, cod, JC-P =3.8 Hz),
(CH=, cod), 76.0 (d, CHCHO, JC-P =5.3 Hz), 77.0 (CH=, cod), 77.2
(CHCH2S), 83.1 (d, CH-O, 2JC-P =15.3 Hz), 101.8 (d, CH=, cod, JC-P =16.1
Hz), 103.8 (d, CH=, cod, JC-P =17.5 Hz), 111.8 (CMe2), 117.4-149.8
1
(aromatic carbons), 161.6 (q, C-B, BArF, JC-B =50.5 Hz). MS HR-ESI
[found 1137.5207, C56H85IrO6PSSi (M)+ requires 1137.5203].
t
t
t
t
t
t
[Ir(cod)(L14a)]BArF. Yield: 69 mg (91%). 31P NMR (161.9 MHz, CDCl3):
δ=102.3 (s). 1H NMR (400 MHz, CDCl3): δ=-0.03 (s, 3H, CH3, OTBDMS),
35.1 (C, Bu), 35.2 (C, Bu), 35.6 (C, Bu), 36.2 (C, Bu), 46.5 (CH2-S),
2
69.5 (CH=, cod), 77.5 (CH=, cod), 78.7 (CHCH2S), 81.3 (d, CH-O, JC-P
=14.5 Hz), 83.6 (d, CHCHO, JC-P =6.0 Hz), 102.1 (d, CH=, cod, JC-P
3
t
-0.02 (s, 3H, CH3, OTBDMS), 0.89 (s, 9H, CH3, Bu, OTBDMS), 1.26 (s,
6H, CH3), 1.37 (s, 9H, CH3, tBu), 1.38 (s, 9H, CH3, tBu), 1.54 (s, 9H, CH3,
=15.3 Hz), 103.9 (d, CH=, cod, JC-P =16.8 Hz), 111.9 (CMe2), 120.8-
1
tBu), 1.77 (s, 9H, CH3, Bu), 1.82 (b, 2H, CH2, cod), 1.99 (b, 3H, CH2-
t
150.7 (aromatic carbons), 162.1 (q, C-B, BArF, JC-B =49.3 Hz). MS HR-
ESI [found 1057.4547, C54H73IrO5PS (M)+ requires 1057.4546].
OTBDMS, CH2, cod), 2.13 (b, 3H, CH2, cod), 2.37 (b, 1H, CH2, cod), 3.23
(d, 1H, CH2-OTBDMS, JH-H =12.0 Hz), 3.81 (d, 1H, CH2-S, JH-H =11.8
2
2
[Ir(cod)(L12f)]BArF. Yield: 65 mg (91%). 31P NMR (161.9 MHz, CDCl3):
Hz), 3.99 (dd, 1H, CH2-S, JH-H =12.8 Hz, JH-H =6.4 Hz), 4.13 (m, 1H,
CH=, cod), 4.26 (pt, 1H, CHCHO, 3JH-H =8.4 Hz), 4.36-4.41 (m, 2H, CH-O,
CH=, cod), 4.61 (b, 1H, CHCH2S), 4.98 (b, 1H, CH=, cod), 5.07 (b, 1H,
CH=, cod), 7.12-8.07 (m, 23H, CH= aromatic). 13C NMR (100.6 MHz,
CDCl3): δ=-5.7 (CH3, SiMe3, OTBDMS), -5,0 (CH3, SiMe3, OTBDMS),
18.3 (C, Bu, OTBDMS), 25.8 (CH3, Bu, OTBDMS), 26.5 (CH3), 26.8
(CH3), 27.7 (CH2, cod), 29.7 (CH2, cod), 30.9 (CH3, tBu), 31.2 (CH3, tBu),
31.4 (CH3, tBu), 31.7 (CH2, cod), 31.9 (CH3, tBu), 33.6 (CH2, cod), 34.8 (C,
tBu), 35.0 (C, Bu), 35.2 (C, Bu), 35.9 (C, Bu), 45.8 (CH2-S), 60.5 (CH2-
OTBDMS), 68.8 (CH=, cod), 76.1 (d, CHCHO, JC-P =4.5 Hz), 77.2
(CHCH2S, CH= cod), 83.2 (d, CH-O, 2JC-P =14.5 Hz), 101.9 (d, CH=, cod,
JC-P =14.6 Hz), 103.8 (d, CH=, cod, JC-P =16.9 Hz), 111.8 (CMe2), 117.4-
2
3
3
δ=102.9 (s). 1H NMR (400 MHz, CDCl3): δ=0.45 (d, 3H, CH3, JH-H =6.4
Hz), 0.57 (s, 9H, CH3, SiMe3), 0.86 (s, 9H, CH3, SiMe3), 1.26 (s, 3H,
CH3), 1.30 (s, 3H, CH3), 1.62 (b, 2H, CH2, cod), 1.95 (m, 1H, CH2, cod),
2.00 (b, 4H, CH2, cod), 2.20 (m, 1H, CH2, cod), 3.27 (b, 1H, CH=, cod),
4.01 (m, 2H, CH2-S, CHCHO), 4.19 (dd, 1H, CH2-S, 2JH-H =14.4 Hz, 3JH-H
=6.0 Hz), 4.30 (m, 2H, CH-O, CHCH2S), 4.57 (b, 2H, CH=, cod), 4.71 (b,
1H, CH=, cod), 7.02-8.24 (m, 29H, CH= aromatic). 13C NMR (100.6 MHz,
CDCl3): δ=0.28 (CH3, SiMe3), 1.93 (CH3, SiMe3), 18.7 (CH3), 26.8 (CH3),
26.9 (CH3), 30.1 (b, CH2, cod), 30.4 (b, CH2, cod), 31.2 (b, CH2, cod),
35.3 (d, CH2, cod, JC-P =4.6 Hz), 48.8 (CH2-S), 70.3 (CH=, cod), 77.6
t
t
t
t
t
3
2
(CH=, cod), 80.5 (CHCH2S), 82.7 (CHCHO), 84.7 (d, CH-O, JC-P =20.1
1
Hz), 101.4 (d, CH=, cod, JC-P =17.5 Hz), 103.4 (d, CH=, cod, JC-P =15.3
Hz), 110.2 (CMe2), 120.8-150.7 (aromatic carbons), 162.1 (q, C-B, BArF,
1JC-B =49.3 Hz). MS HR-ESI [found 1077.3148, C52H61IrO5PSSi2 (M)+
requires 1077.3145].
149.8 (aromatic carbons), 161.7 (q, C-B, BArF, JC-B =49.7 Hz). MS HR-
ESI [found 1087.5363, C60H87IrO6PSSi (M)+ requires 1087.5359].
[Ir(cod)(L15g)]BArF. Yield: 73 mg (90%).31P NMR (161.9 MHz, CDCl3):
δ=100.5 (s). 1H NMR (400 MHz, CDCl3): δ=0.55 (s, 9H, CH3, SiMe3),
0.70 (s, 9H, CH3, SiMe3), 1.09 (s, 9H, CH3, Bu, OTBDPS), 1.18 (s, 3H,
CH3), 1.30 (s, 3H, CH3), 1.70 (b, 1H, CH2, cod), 1.85 (b, 2H, CH2, cod),
2.01 (b, 1H, CH2, cod), 2.11-2.22 (m, 3H, CH2, cod), 2.30-2.36 (m, 1H,
CH2, cod), 2.51 (d, 1H, CH2-OTBDPS, 2JH-H =12.0 Hz), 3.37 (d, 1H, CH2-
[Ir(cod)(L12g)]BArF. Yield: 64 mg (89%). 31P NMR (161.9 MHz, CDCl3):
δ= 99.6 (s). 1H NMR (400 MHz, CDCl3): δ=0.56 (b, 3H, CH3), 0.58 (s, 9H,
CH3, SiMe3), 0.73 (s, 9H, CH3, SiMe3), 1.29 (s, 3H, CH3), 1.34 (s, 3H,
CH3), 1.74-1.81 (b, 2H, CH2, cod), 1.89-2.05 (m, 3H, CH2, cod), 2.16-
2.36 (b, 3H, CH2, cod), 3.59 (b, 1H, CH=, cod), 3.62 (m, 1H, CH2-S), 3.94
(pt, 1H, CHCHO, 3JH-H =7.2 Hz), 4.02 (dd, 1H, CH2-S, 2JH-H =11.6 Hz, 3JH-
t
2
OTBDPS, JH-H =11.6 Hz), 3.44-3.49 (m, 1H, CH2-S), 3.74 (b, 1H, CH=,
cod), 4.11 (d, 1H, CH2-S, JH-H =9.9 Hz), 4.32 (b, 2H, CH-O, CH=, cod),
2
=3.2 Hz), 4.36 (m, 1H, CH=, cod), 4.46 (m, 1H, CH-O), 4.55 (m, 1H,
4.68 (b, 2H, CHCH2S, CHCHO), 4.97 (b, 1H, CH=, cod), 5.34 (b, 1H,
H
CHCH2S), 4.83 (b, 1H, CH=, cod), 5.19 (b, 1H, CH=, cod), 7.00-8.19 (m,
29H, CH= aromatic). 13C NMR (100.6 MHz, CDCl3): δ=0.44 (CH3, SiMe3),
1.21 (CH3, SiMe3), 19.3 (CH3), 26.6 (CH3), 27.0 (CH3), 28.2 (CH2, cod),
29.5 (CH2, cod), 32.4 (CH2, cod), 33.3 (CH2, cod), 46.2 (CH2-S), 69.7
(CH=, cod), 69.5 (CH=, cod), 79.0 (CHCH2S), 80.0 (CH=, cod), 80.1 (CH-
O), 82.9 (d, CHCHO, 2JC-P =20.1 Hz), 101.4 (d, CH=, cod, JC-P =17.5 Hz),
103.4 (d, CH=, cod, JC-P =15.3 Hz), 110.2 (CMe2), 120.8-150.7 (aromatic
CH=, cod), 6.93-8.17 (m, 39H, CH= aromatic). 13C NMR (100.6 MHz,
t
CDCl3): δ=-0.1 (CH3, SiMe3), -0.8 (CH3, SiMe3), 19.8 (C, Bu, OTBDPS),
t
26.0 (CH3), 26.7 (CH3), 27.1 (CH3, Bu, OTBDPS), 27.7 (CH2, cod), 29.8
(CH2, cod), 31.8 (CH2, cod), 33.6 (CH2, cod), 45.6 (CH2-S), 62.5 (CH2-
OTBDPS), 70.0 (CH=, cod), 75.7 (CHCHO, CHCH2S), 80.0 (CH=, cod),
82.2 (d, CH-O, 2JC-P =14.6 Hz), 102.6 (d, CH=, cod, JC-P =16.0 Hz), 105.6
(d, CH=, cod, JC-P =16.0 Hz), 112.4 (CMe2), 117.4-151.0 (aromatic
1
1
carbons), 162.1 (q, C-B, BArF, JC-B =49.3 Hz). MS HR-ESI [found
carbons), 161.8 (q, C-B, BArF, JC-B =49.7 Hz). MS HR-ESI [found
1077.3147, C52H61IrO5PSSi2 (M)+ requires 1077.3145].
1331.4276, C68H79IrO6PSSi3 (M)+ requires 1331.4272].
[Ir(cod)(L13a)]BArF. Yield: 66 mg (89%). 31P NMR (161.9 MHz, CDCl3):
δ=102.1 (s). 1H NMR (400 MHz, CDCl3): δ=-0.04 (s, 3H, CH3, OTBDMS),
[Ir(cod)(L16g)]BArF. Yield: 71 mg (91%). 31P NMR (161.9 MHz, CDCl3):
δ=100.4 (s). 1H NMR (400 MHz, CDCl3): δ=0.62 (s, 9H, CH3, SiMe3),
0.71 (s, 9H, CH3, SiMe3), 0.97 (s, 21H, CH, CH3, OTIPS), 1.27 (s, 3H,
CH3), 1.38 (s, 3H, CH3), 1.69 (b, 1H, CH2, cod), 1.84 (b, 2H, CH2, cod),
2.00 (b, 1H, CH2, cod), 2.11 (b, 3H, CH2, cod), 2.34 (b, 1H, CH2, cod),
t
0.00 (s, 3H, CH3, OTBDMS), 0.88 (s, 9H, CH3, Bu, OTBDMS), 1.25 (s,
3H, CH3), 1.26 (s, 3H, CH3), 1.35 (s, 9H, CH3, tBu), 1.37 (s, 9H, CH3, tBu),
t
t
1.51 (s, 9H, CH3, Bu), 1.72 (s, 9H, CH3, Bu), 1.86 (b, 2H, CH2, cod),
1.94 (d, 1H, CH2-OTBDMS, 2JH-H =12.0 Hz), 2.04-2.13 (b, 5H, CH2, cod),
2.33-2.38 (m, 1H, CH2, cod), 3.22 (d, 1H, CH2-OTBDMS, 2JH-H =11.6 Hz),
3.73 (dd, 1H, CH2-S, 2JH-H =12.8 Hz, 3JH-H =2.8 Hz), 3.87 (dd, 1H, CH2-S,
2
2
2.51 (d, 1H, CH2-OTIPS, JH-H =11.2 Hz), 3.30 (d, 1H, CH2-OTIPS, JH-H
=10.4 Hz), 3.45-3.50 (m, 1H, CH2-S), 3.72 (b, 1H, CH=, cod), 4.08 (dd,
1H, CH2-S, 2JH-H =10.8 Hz, 3JH-H =2.8 Hz), 4.30-4.38 (m, 2H, CH-O, CH=,
3
3
2JH-H =13.2 Hz, JH-H =6.4 Hz), 4.11 (b, 1H, CH=, cod), 4.23 (pt, 1H,
cod), 4.57 (pt, 1H, CHCHO, JH-H =8.4 Hz), 4.65 (m, 1H, CHCH2S), 4.96
3
CHCHO, JH-H =8.8 Hz), 4.31-4.37 (m, 2H, CH= cod, CH-O), 4.53-4.57
(b, 1H, CH=, cod), 5.31 (b, 1H, CH=, cod), 6.94-8.17 (m, 29H, CH=
aromatic). 13C NMR (100.6 MHz, CDCl3): δ=-0.1 (CH3, SiMe3), 0.8 (CH3,
SiMe3), 12.0 (CH, OTIPS), 17.9 (CH3, OTIPS), 26.2 (CH3), 26.8 (CH3),
27.6 (CH2, cod), 29.8 (b, CH2, cod), 31.8 (CH2, cod), 33.6 (CH2, cod), 45.5
(CH2-S), 62.3 (CH2-OTr), 69.8 (CH=, cod), 76.1 (CHCH2S), 77.0
(m, 1H, CHCH2S), 4.97 (b, 2H, CH=, cod), 7.10-7.71 (m, 21H, CH=
aromatic). 13C NMR (100.6 MHz, CDCl3): δ=-5.7 (CH3, OTBDMS), -5.0
t
t
(CH3, OTBDMS), 18.3 (C, Bu, OTBDMS), 25.8 (CH3, Bu, OTBDMS),
26.5 (CH3), 26.8 (CH3), 27.7 (CH2, cod), 30.8 (CH3, tBu), 30.9 (CH2, cod),
t
t
2
31.2 (CH3, Bu), 31.4 (CH3, Bu), 31.6 (d, CH2, cod, JC-P =3.8 Hz), 31.8
(CH3, Bu), 33.6 (d, CH2, cod, JC-P =4.3 Hz), 34.8 (C, Bu), 34.9 (C, Bu),
35.2 (C, Bu), 35.8 (C, Bu), 45.6 (CH2-S), 60.5 (CH2-OTBDMS), 68.8
(CHCHO), 80.0 (CH=, cod), 82.5 (d, CH-O, JC-P =14.5 Hz), 102.5 (d,
t
t
t
CH=, cod, JC-P =16.8 Hz), 105.3 (d, CH=, cod, JC-P =16.1 Hz), 112.6
(CMe2), 117.4-151.1 (aromatic carbons), 161.7 (q, C-B, BArF, 1JC-B =49.7
t
t
This article is protected by copyright. All rights reserved.