(η4-1,5-Cyclooctadiene) [(Sp)-1-[(1R)-(1-(7-bromo-3H-isobenzo-
furan-1-ylideneamino)-ethyl)]-2-(diphenylphosphino)ferrocene]
iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (11d).
OCH3), 4.08–4.17 (m, 3H, COD), 4.43 (s, 1H, CpH), 4.53 (s,
1H, CpH), 4.90 (s, 1H, CpH), 5.45–5.56 (m, 2H, CH2, imidate),
5.82 (q, J = 6.6 Hz, 1H, CH3CH), 6.94–6.99 (m, 3H, PhH),
7.34–7.36 (m, 4H, PhH imidate), 7.51 (s, 4H, BArF p-H),
7.54–7.56 (m, 3H, PhH), 7.71 (s, 8H, BArF o-H), 8.00–8.06 (m,
2H, PhH), 9.70 (d, J = 8.9 Hz, 1H) ppm. 13C-NMR (75.4 MHz,
CDCl3): δ 25.5 (CH2, J = 1.5 Hz, COD), 27.6 (CH2, COD), 29.9
(CH3), 31.8 (CH2, J = 1 Hz, COD), 36.6 (CH2, J = 4.4 Hz,
COD), 56.1 (CH3, OCH3), 56.6 (CH, CH3CH), 62.3 (CH,
COD), 64.9 (C), 65.7 (C), 67.1 (CH, COD), 69.8 (5 × CH,
CpH), 70.3 (CH, J = 8.8 Hz, CpH), 71.0 (CH, J = 1.6 Hz,
COD), 71.2 (CH, J = 6.8 Hz, CpH), 73.6 (CH2, OCH2), 92.6
(CH, J = 14.1 Hz, COD), 98.6 (CH, J = 9.6 Hz, CpH), 101.3
(C), 101.5 (C), 106.1 (CH, PhH), 117.0 (CH, PhH), 117.4–117.5
(4 × CH, m, BArF p-C), 117.8 (C), 119.1 (C), 122.7 (C), 126.4
(C), 128.2–128.3 (C, m), 128.5 (CH, J = 9.9 Hz, PhH), 128.7
(C, J = 3.0 Hz), 129.0 (CH, J = 11.0 Hz, PhH), 129.0 (C), 129.1
(C, J = 2.9 Hz), 129.4–129.5 (C, m), 129.7 (CH, PhH), 130.0
(C), 130.6 (CH, J = 2.0 Hz, PhH), 131.4 (CH, J = 9.4 Hz, PhH),
132.2 (CH, J = 2.0 Hz, PhH), 133.0 (C, J = 8.9 Hz), 133.9 (C),
134.8 (8 × CH, m, BArF o-C), 135.0 (CH, PhH), 148.8 (C),
160.7 (C), 161.4 (C), 162.0 (C), 162.7 (C), 165.1 (C), 167.8 (C)
ppm. 31P-NMR (121.4 MHz, CDCl3): δ 6.9 ppm. IR (HATR):
2912, 2160, 1992, 1607, 1487, 1352, 1337, 1302, 1272, 1116,
1
Yield: 119.8 mg (69%). H-NMR (300 MHz, CDCl3): complex
spectrum, copy at the end of the ESI.† 13C-NMR (75.4 MHz,
CDCl3): complex spectrum, copy at the end of the ESI.†
31P-NMR (121.4 MHz, CDCl3): δ 8.2, 4.0, 1.5, −2.4, −3.2,
−5.7 ppm (6 peaks are observed due to the presence of several
conformers). IR (HATR): 2922, 1647, 1612, 1523, 1435, 1352,
1337, 1308, 1304, 1296, 1273, 1116, 946, 885, 854, 837, 774,
726, 714, 709, 694, 688, 681, 673, 669 cm−1. ES-MS: m/z 908.0
[M − BArF−]+.
(η4-1,5-Cyclooctadiene)
[(Sp)-1-[(1R)-(1-(5,6-dimethoxy-3H-
isobenzofuran-1-ylideneamino)-ethyl)]-2-(diphenylphosphino)ferro-
cene] iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate
(11e). Yield: 261.1 mg (88%).1H-NMR (300 MHz, CDCl3): δ
1.19–1.32 (m, 1H, COD), 1.59–1.70 (m, 2H, COD), 2.00–2.11
(m, 1H, COD), 2.2 (d, J = 6.Hz, 2H, CH3), 2.25–2.32 (m, 2H,
COD), 2.35–2.37 (m, 1H, COD), 2.45–2.53 (m, 1H, COD),
2.64–2.78 (m, 1H, COD), 3.30 (s, 5H, CpH), 3.91–3.93 (m, 1H,
COD), 3.97 (s, 3H, OCH3), 4.15 (s, 1H, COD), 4.31 (s, 3H,
OCH3), 4.36–4.41 (m, 1H, COD), 4.44 (t, J = 2.5 Hz, 1H,
CpH), 4.55 (s, 1H, CpH), 4.85 (s, 1H, CpH), 5.41–5.53 (m, 2H,
CH2, imidate), 5.90 (q, J = 6.7 Hz, 1H, CH3CH), 6.92–6.98 (m,
3H, PhH), 7.31–7.38 (m, 3H, PhH imidate), 7.51 (s, 4H, BArF
p-H), 7.57–7.62 (m, 3H, PhH), 7.71 (s, 8H, BArF o-H),
8.13–8.19 (m, 2H, PhH), 8.9 (s, 1H, PhH) ppm. 13C-NMR
(75.4 MHz, CDCl3): δ 25.9 (CH2, J = 1.8 Hz, COD), 27.8 (CH2,
J = 1.1 Hz, COD), 29.7 (CH3), 31.3 (CH2, J = 1.2 Hz, COD),
36.6 (CH2, J = 4.3 Hz, COD), 56.5 (CH3, OCH3), 57.0 (CH,
CH3CH), 57.5 (CH3, OCH3), 60.6 (CH, COD), 64.7 (C), 65.4
(C), 66.9 (CH, COD), 69.8 (5 × CH, CpH), 70.5 (CH, J = 8.9
Hz, CpH), 70.9 (CH, J = 1.8 Hz, COD), 71.2 (CH, J = 6.9 Hz,
CpH), 73.3 (CH2, OCH2), 91.5 (CH, J = 14.4 Hz, COD), 98.0
(CH, J = 10.3 Hz, CpH), 101.4 (C), 101.7 (C), 104.0 (CH,
PhH), 110.4 (CH, PhH), 117.3 (C), 117.4–117.5 (4 × CH, m,
BArF p-C), 119.1 (C), 122.7 (C), 126.3 (C), 128.2–128.3 (C, m),
128.5 (CH, J = 9.9 Hz, PhH), 128.6 (C, J = 8.9 Hz), 128.9 (CH,
J = 10.9 Hz, PhH), 129.0–129.1 (C, m), 129.4–129.6 (C, m),
130.0 (C), 130.7 (CH, J = 2.6 Hz, PhH), 131.4 (CH, J = 9.4 Hz,
PhH), 131.8 (C), 132.4 (CH, J = 2.3 Hz, PhH), 132.6 (C), 133.4
(C), 134.1 (C), 134.8 (8 × CH, m, BArF o-C), 134.9 (CH, PhH),
135.1 (CH, PhH), 141.7 (C), 151.0 (C), 156.1 (C), 160.7 (C),
161.4 (C), 162.0 (C), 162.9 (C), 168.3 (C) ppm. 31P-NMR
(121.4 MHz, CDCl3): δ +6.8 ppm. IR (HATR): 2890, 1610,
1498, 1461, 1353, 1296, 1273, 1228, 1118, 1081, 1059, 1032,
1001, 886, 839, 744, 712, 682, 669 cm−1. ES-MS: m/z 890.1
[M − BArF−]+. [α]D20 = +20.3 (c 0.98, CHCl3). HRMS (ES):
calcd for C42H44Fe193IrNO3P: 890.2037; found: 890.2032.
1061, 1030, 885, 840, 745, 730, 696, 682, 669, 621 cm−1
.
ES-MS: m/z 860.1 [M − BArF−]+. [α]D20 = +42.9 (c 1.05,
CHCl3). HRMS (ES): calcd for C41H42Fe193IrNO2P: 860.1932;
found: 860.1929.
(η4-1,5-Cyclooctadiene) [(Sp)-1-[(1R)-(1-(6-methyl-3H-isobenzo-
furan-1-ylideneamino)-ethyl)]-2-(diphenylphosphino)ferrocene]
iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (11g).
Yield: 269 mg (91%). 1H-NMR (300 MHz, CDCl3): δ 1.29–1.35
(m, 1H, COD), 1.58–1.69 (m, 2H, COD), 1.98–2.05 (m, 1H,
COD), 2.17 (d, J = 6.8 Hz, 2H, CH3), 2.22–2.25 (m, 2H, COD),
2.32–2.41 (m, 1H, COD), 2.44–2.52 (m, 1H, COD), 2.78 (s, 3H,
CH3), 2.82–2.90 (m, 1H, COD), 3.28 (s, 5H, CpH), 4.12–4.18
(m, 3H, COD), 4.45 (t, J = 2.4 Hz, 1H, CpH), 4.54 (s, 1H,
CpH), 4.88 (s, 1H, CpH), 5.60–5.62 (m, 2H, CH2, imidate), 5.87
(q, J = 6.8 Hz, 1H, CH3CH), 6.93–6.99 (m, 2H, PhH),
7.32–7.39 (m, 4H, PhH imidate), 7.51 (s, 4H, BArF p-H),
7.54–7.60 (m, 4H, PhH), 7.72 (s, 8H, BArF o-H), 8.08–8.14 (m,
2H, PhH), 9.74 (s, 1H) ppm. 13C-NMR (75.4 MHz, CDCl3): δ
21.1 (CH3), 25.6 (CH2, J = 2.1 Hz, COD), 27.5 (CH2, J =
1.7 Hz, COD), 29.8 (CH3), 31.7 (CH2, COD), 36.7 (CH2, J =
5.1 Hz, COD), 57.0 (CH, CH3CH), 62.3 (CH, COD), 64.8 (C),
65.5 (C), 67.1 (CH, COD), 69.8 (5 × CH, CpH), 70.3 (CH, J =
8.8 Hz, CpH), 71.1 (CH, J = 1.7 Hz, COD), 71.3 (CH, J =
7.1 Hz, CpH), 74.2 (CH2, OCH2), 92.1 (CH, J = 14.8 Hz,
COD), 98.6 (CH, J = 10.7 Hz, CpH), 101.2 (C), 101.5 (C),
117.4–117.5 (4 × CH, m, BArF p-C), 119.1 (C), 122.4 (CH,
PhH), 122.7 (C), 126.3 (C, J = 8.4 Hz), 128.2–128.3 (C, m),
128.4 (CH, J = 8.2 Hz, PhH), 128.6 (C), 128.7 (CH, PhH),
128.7 (C, J = 2.7 Hz), 128.9 (CH, J = 10.9 Hz, PhH),
129.1–129.2 (C, m), 129.5–129.6 (C, m), 130.0 (C), 130.7 (CH,
J = 2.2 Hz, PhH), 131.4 (CH, J = 9.3 Hz, PhH), 132.1 (C),
132.3 (CH, J = 2.2 Hz, PhH), 132.9 (C, J = 9.3 Hz), 133.8 (C),
134.8–134.9 (8 × CH, m, BArF o-C), 135.1 (CH, PhH), 135.8
(CH, PhH), 139.6 (C), 143.2 (C), 160.7 (C), 161.4 (C), 162.1 (C),
(η4-1,5-Cyclooctadiene)
[(Sp)-1-[(1R)-(1-(5-methoxy-3H-iso-
benzofuran-1-ylideneamino)-ethyl)]-2-(diphenylphosphino)ferro-
cene] iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate
1
(11f). Yield: 272.3 mg (88%). H-NMR (300 MHz, CDCl3): δ
1.29–1.32 (m, 1H, COD), 1.59–1.68 (m, 2H, COD), 1.97–2.08
(m, 1H, COD), 2.13 (d, J = 6.6 Hz, 2H, CH3), 2.19–2.24 (m,
2H, COD), 2.32–2.37 (m, 1H, COD), 2.40–2.45 (m, 1H, COD),
2.67–2.81 (m, 1H, COD), 3.29 (s, 5H, CpH), 3.92 (s, 3H,
8548 | Org. Biomol. Chem., 2012, 10, 8539–8550
This journal is © The Royal Society of Chemistry 2012