Iridium Phosphite-Oxazoline Catalysts
A R T I C L E S
[Ir(cod)(L4a)]BArF. Yield: 122 mg (92%). 31P NMR (CDCl3)
δ ) 102.0 (s). 1H NMR (CDCl3) δ ) 1.37 (s, 9H, CH3, tBu), 1.38
(s, 9H, CH3, tBu), 1.55 (s, 9H, CH3, tBu), 1,61 (b, 4H, CH2, cod)
1.72 (s, 9H, CH3, tBu), 2.17 (m, 3H, CH2, cod), 2.33 (b, 1H, CH2,
cod), 2.36 (s, 3H, CH3-Ph), 3.47 (m, 1H, CHd, cod), 4.26 (b,
5H, CH-N, CH2-O, CH2-OP and CHd, cod), 4.83 (b, 2H, CH2-O
and CHd, cod), 5.27 (b, 1H, CHd, cod), 7.1 - 8.3 (m, 20H,
aromatics). 13C NMR (CDCl3) δ ) 25.6 (b, CH2, cod), 29.3 (b,
CH2, cod), 31.3 (CH3, tBu), 31.5 (CH3, tBu), 31.6 (b, CH3, tBu),
32.4 (b, CH2, cod), 34.9 (C, tBu), 35.0 (C, tBu), 35.5 (b, CH2, cod),
36.0 (C, tBu), 36.1 (CH3-Ph), 36.2 (C, tBu), 65.1 (CH), 66.0
(CHd, cod), 69.0 (CH2-O), 72.2 (CHd, cod), 70.7 (CH2-OP),
(aromatic carbons), 135.0 (b, CHd, BArF), 136-149 (aromatic
1
carbons), 161.9 (q, C-B, BArF, JC-B ) 49.8 Hz), 176.6 (CdN).
Anal. Calc (%) for C82H82BF24IrNO4P: C 53.66, H 4.50, N 0.76;
found: C 53.69, H 4.47, N 0.73.
[Ir(cod)(L10a)]BArF. Yield: 119 mg (90%). 31P NMR (CDCl3)
1
δ ) 102.5 (s). H NMR (CDCl3) δ ) 1.16 (s, 3H, CH3), 1.27 (s,
3H, CH3), 1.34 (s, 9H, CH3, tBu), 1.37 (s, 9H, CH3, tBu), 1.54 (s,
9H, CH3, tBu), 1.55 (s, 18H, CH3, tBu and tBu-CdN), 1.71 (m,
4H, CH2, cod), 2.07 (m, 1H, CH2, cod), 2.20 (m, 1H, CH2, cod),
2.37 (m, 1H, CH2, cod), 2.55 (m, 1H, CH2, cod), 4.09 (m, 1H,
2
3
CHd, cod), 4.16 (dd, 1H, CH2, JH-H ) 10.5 Hz, JH-H ) 3 Hz),
4.25 (t, 1H, CH2, 2JH-H ) 10.5), 4.51 (b, 2H, CH and CHd, cod),
4.76 (b, 1H, CHd, cod), 5.36 (b, 1H, CHd, cod), 7.1 - 7.8 (m.
16H, aromatics). 13C NMR (CDCl3) δ ) 21.1 (CH3), 24.5 (b, CH2,
cod), 26.4 (CH3), 28.3 (b, CH2, cod), 29.4 (CH3, tBu), 31.2 (CH3,
tBu), 31.3 (CH3, tBu), 31.5 (CH3, tBu), 31.6 (CH3, tBu), 34.5 (C,
tBu), 34.7 (b, CH2, cod), 34.9 (C, tBu), 35.3 (C, tBu), 35.8 (C,
tBu), 37.6 (b, CH2, cod), 69.1 (CHd, cod), 69.5 (CHd, cod), 69.6
(CH2), 74.8 (CH), 83.8 (d, CMe2, JC-P ) 5.7 Hz), 89.6 (d, CHd,
cod, JC-P ) 26.2 Hz), 103.1 (d, CHd, cod, JC-P ) 10.5 Hz), 117.7
(b, CHd, BArF), 119-131 (aromatic carbons), 135.0 (b, CHd,
99.0 (d, CHd, cod, JC-P ) 20.2 Hz), 106.8 (d, CHd, cod, JC-P
)
13.7 Hz), 117.7 (b, CHd, BArF), 119-134 (aromatic carbons),
135.0 (b, CHd, BArF), 136-149 (aromatic carbons), 161.9 (q,
1
C-B, BArF, JC-B ) 49.5 Hz), 174.4 (CdN). Anal. Calc (%) for
C79H76BF24IrNO4P: C 52.91, H 4.27, N 0.78; found: C 52.33, H
4.20, N 0.75.
[Ir(cod)(L5d)]BArF. Yield: 109 mg (93%). 31P NMR (CDCl3)
1
δ ) 102.4 (s). H NMR (CDCl3) δ ) 1.29 (s, 3H, CH3), 1.36 (s,
3H, CH3), 1.67 (m, 3H, CH2, cod), 2.22 (m, 2H, CH2, cod), 2.40
(m, 3H, CH2, cod), 3.58 (m, 1H, CHd, cod), 3.94 (b, 1H, CHd,
cod), 4.58 (dd, 1H, CH2, 2JH-H ) 10.2 Hz, 3JH-H ) 3 Hz), 4.73 (t,
1H, CH2, 2JH-H ) 9 Hz), 4.90 (dd, 1H, CH, 3JH-H ) 8.7 Hz, 3JH-H
) 2.4 Hz), 5.00 (b, 1H, CHd, cod), 5.42 (b, 1H, CHd, cod), 7.1
- 7.8 (m, 25H, aromatics). 13C NMR (CDCl3) δ ) 20.9 (CH3),
25.4 (b, CH2, cod), 27.0 (CH3), 29.3 (b, CH2, cod), 32.1 (b, CH2,
cod), 36.9 (b, CH2, cod), 66.1 (CHd, cod), 68.0 (CHd, cod), 70.6
(CH2), 73.6 (CH), 86.0 (d, CMe2, JC-P ) 6.5 Hz), 100.4 (d, CHd,
cod, JC-P ) 18.7 Hz), 108.8 (d, CHd, cod, JC-P ) 14.0 Hz), 117.7
(b, CHd, BArF), 119-132 (aromatic carbons), 135.0 (b, CHd,
1
BArF), 136-150 (aromatic carbons), 161.9 (q, C-B, BArF, JC-B
) 49.8 Hz), 183.9 (CdN). Anal. Calc (%) for C78H82BF24IrNO4P:
C 52.41, H 4.62, N 0.78; found: C 52.38, H 4.60, N 0.75.
[Ir(cod)(L11a)]BArF. Yield:125 mg (88%). 31P NMR (CDCl3)
1
δ ) 98.3 (s). H NMR (CDCl3) δ ) 1.16 (b, 3H, CH3), 1.28 (b,
3H, CH3), 1.39 (b, 18H, CH3, tBu), 1.55 (b, 18H, CH3, tBu), 1.69
(b, 3H, CH2, cod), 2.27 (b, 3H, CH2, cod), 2.46 (b, 2H, CH2, cod),
4.01 (b, 1H, CHd, cod), 4.30 (b, 9H, CHd, Cp), 4.50 (b, 2H, CHd,
cod), 4.70 (b, 2H, CH2), 4.90 (b, 1H, CH), 5.23 (b, 1H, CHd, cod),
5.42 (b, 1H, CHd, cod), 7.1 - 7.8 (m, 16H, aromatics). 13C NMR
(CDCl3) δ ) 22.0 (b, CH2, cod), 28.8 (b, CH2, cod), 31.5 (CH3,
tBu), 31.6 (CH3, tBu), 31.9 (CH3, tBu), 32.1 (CH3, tBu), 33.7 (b,
CH2, cod), 34.9 (C, tBu), 35.0 (C, tBu), 35.4 (C, tBu), 35.9 (C,
tBu), 37.0 (b, CH2, cod), 67.5 (CHd, cod), 70.4 (CHd, cod), 71.0
(b, CHd, Cp), 71.9 (CH2), 73.8 (CH), 84.9 (b, CMe2), 95.0 (CHd,
cod), 100.9 (CHd, cod), 117.7 (b, CHd, BArF), 119-131 (aromatic
carbons), 135.0 (b, CHd, BArF), 136-150 (aromatic carbons),
161.9 (q, C-B, BArF, 1JC-B ) 49.8 Hz), 176.9 (CdN). Anal. Calc
(%) for C84H82BF24FeIrNO4P: C 52.67, H 4.32, N 0.73; found: C
52.78, H 4.34, N 0.74.
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BArF), 136-150 (aromatic carbons), 161.9 (q, C-B, BArF, JC-B
) 49.5 Hz), 172.6 (CdN). Anal. Calc (%) for C64H46BF24IrNO4P:
C 48.56, H 2.93, N 0.88; found: C 48.63, H 2.98, N 0.90.
[Ir(cod)(L8a)]BArF. Yield: 129 mg (96%). 31P NMR (CDCl3)
1
δ ) 96.2 (s). H NMR (CDCl3) δ ) 1.08 (s, 3H, CH3), 1.27 (s,
3H, CH3), 1.36 (s, 9H, CH3, tBu), 1.38 (s, 9H, CH3, tBu), 1.54 (s,
9H, CH3, tBu), 1.72 (s, 9H, CH3, tBu), 1.62 (b, 4H, CH2, cod),
2.11 (m, 2H, CH2, cod), 2.24 (b, 2H, CH2, cod), 2.36 (s, 3H,
CH3-Ph), 3.42 (m, 1H, CHd, cod), 4.19 (b, 1H, CHd, cod), 4.33
2
3
(b, 1H, CHd, cod), 4.48 (dd, 1H, CH2, JH-H ) 9.3 Hz, JH-H
)
2.7 Hz), 4.70 (m, 2H, CH and CH2), 5.19 (b, 1H, CHd, cod), 7.1
- 8.4 (m, 20H, aromatics). 13C NMR (CDCl3) δ ) 20.6 (CH3),
21.6 (b, CH2, cod), 25.4 (CH3), 26.9 (b, CH2, cod), 29.2 (b, CH2,
cod), 31.2 (CH3-Ph), 31.3 (CH3, tBu), 31.4 (CH3, tBu), 31.6 (b,
CH3, tBu), 34.9 (C, tBu), 35.0 (C, tBu), 35.4 (b, CH2, cod), 35.8
(C, tBu), 36.0 (C, tBu), 65.0 (CHd, cod), 69.5 (CHd, cod), 70.6
[Ir(cod)(L12a)]BArF. Yield 123 mg (92%). 31P NMR (CDCl3)
δ ) 97.8 (s). 1H NMR (CDCl3) δ ) 1.06 (s, 3H, CH3), 1.29 (s,
3H, CH3), 1.35 (s, 9H, CH3, tBu), 1.38 (s, 9H, CH3, tBu), 1.54 (s,
9H, CH3, tBu), 1.61 (s, 9H, CH3, tBu), 1.70 (m, 4H, CH2, cod),
2.32 (m, 3H, CH2, cod), 2.51 (m, 1H, CH2, cod), 3.60 (b, 1H, CHd,
cod), 4.41 (m, 2H, CHd, cod and CH2), 4.58 (b, 2H, CHd, cod
3
3
(CH2), 72.7 (CH), 84.6 (b, C, CMe2), 98.5 (d, CHd, cod, JC-P
)
and CH2), 4.67 (dd, 1H, CH, JH-H ) 10. 0 Hz, JH-H ) 3.2 Hz),
5.32 (b, 1H, CHd, cod), 7.1-8.5 (m, 21H, CHd, aromatics). 13C
NMR (CDCl3) δ ) 21.3 (CH3), 24.8 (b, CH2, cod), 26.5 (m, CH3),
28.09 (b, CH2, cod), 31.2 (CH3, tBu), 31.4 (CH3, tBu), 31.6 (CH3,
tBu), 33.2 (b, CH2, cod), 34.8 (C, tBu), 34.9 (C, tBu), 35.2 (C,
tBu), 37.3 (b, CH2, cod), 66.3 (CHd, cod), 69.8 (CHd, cod), 70.0
(CH2), 71.2 (CH), 84.9 (d, CMe2, JC-P ) 5.2 Hz), 93.5 (d, CHd,
cod, JC-P ) 21.1 Hz), 106.3 (d, CHd, cod, JC-P ) 6.2 Hz), 117.7
(b, CHd, BArF), 119-132 (aromatic carbons), 135.0 (b, CHd,
BArF), 135.5-150 (aromatic carbons), 161.9 (q, C-B, BArF, 1JC-B
) 48.6 Hz), 173.7 (CdN). Anal. Calc (%) for C80H78BF24IrNO4P:
C 53.16, H 4.35, N 0.77; found: C 53.22, H 4.40, N 0.76.
19.9 Hz), 106.8 (b, CHd, cod), 117.7 (b, CHd, BArF), 119-134
(aromatic carbons), 135.0 (b, CHd, BArF), 136-149 (aromatic
1
carbons), 161.9 (q, C-B, BArF, JC-B ) 49.5 Hz), 175.1 (CdN).
Anal. Calc (%) for C81H80BF24IrNO4P: C 53.41, H 4.43, N 0.77;
found: C 53.48, H 4.39, N 0.83.
[Ir(cod)(L9a)]BArF. Yield: 124 mg (91%). 31P NMR (CDCl3)
1
δ ) 94.1 (s). H NMR (CDCl3) δ ) 1.12 (s, 3H, CH3), 1.30 (s,
3H, CH3), 1.35 (s, 9H, CH3, tBu), 1.37 (s, 9H, CH3, tBu), 1.58 (s,
9H, CH3, tBu), 1.59 (s, 9H, CH3, tBu), 1.72 (b, 4H, CH2, cod),
2.02 (m, 2H, CH2, cod), 2.15 (b, 2H, CH2, cod), 2.26 (s, 3H,
CH3-Ph), 2.80 (s, 3H, CH3-Ph), 3.70 (m, 1H, CHd, cod), 4.01
(b, 2H, CHd, cod), 4.42 (dd, 1H, CH2, 2JH-H ) 10.2 Hz, 3JH-H
)
[Ir(cod)(L14a)]BArF. Yield: 124 mg (92%). 31P NMR (CDCl3)
2
1
5.1 Hz), 4.27 (t, 1H, CH2, JH-H ) 10.5 Hz), 4.51 (dd, 1H, CH,
2JH-H ) 10.8 Hz, 3JH-H ) 5.1 Hz), 5.19 (b, 1H, CHd, cod), 7.1 -
7.9 (m, 19H, aromatics). 13C NMR (CDCl3) δ ) 20.5 (CH3), 22.6
(b, CH2, cod), 23.3 (CH3), 27.7 (b, CH2, cod), 29.7 (b, CH2, cod),
31.2 (CH3-Ph), 31.4 (CH3, tBu), 31.6 (b, CH3, tBu), 34.9 (C, tBu),
35.0 (b, CH2, cod), 35.2 (C, tBu), 35.4 (b, C, tBu), 35.8 (CH3-Ph),
63.9 (CHd, cod), 66.0 (CHd, cod), 69.3 (CH2), 74.0 (CH), 83.5
(b, C, CMe2), 103.4 (d, CHd, cod, JC-P ) 18.0 Hz), 106.0 (d,
CHd, cod, JC-P ) 10.5 Hz), 117.7 (b, CHd, BArF), 119-134
δ ) 99.1 (s). H NMR (CDCl3) δ ) 1.12 (s, 3H, CH3), 1.31 (s,
3H, CH3), 1.37 (b, 18H, CH3, tBu), 1.57 (s, 9H, CH3, tBu), 1.63
(s, 9H, CH3,tBu), 1.70 (b, 4H, CH2, cod), 2.15 (s, 3H, CH3), 2.33
(b, 3H, CH2, cod), 2.55 (b, 1H, CH2, cod), 3.65 (b, 1H, CHd, cod),
3.65 (b, 1H, CHd, cod), 4.22 (b, 1H, CH-N), 4.41 (b, 1H, CHd,
cod), 4.41 (b, 1H, CHd, cod), 4.61 (b, 1H, CHd, cod), 4.74 (b,
1H, CH-O), 5.25 (b, 1H, CHd, cod), 7.1 - 8.4 (m, 21H,
aromatics). 13C NMR (CDCl3) δ ) 21.0 (CH3), 21.8 (CH3), 24.9
(b, CH2, cod), 26.2 (b, CH2, cod), 28.9 (b, CH2, cod), 31.3 (CH3,
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J. AM. CHEM. SOC. VOL. 131, NO. 34, 2009 12351