C. Metallinos, L. Van Belle / Journal of Organometallic Chemistry 696 (2011) 141e149
147
which time the color changed from orange to red. The layers were
separated, the aqueous layer extracted with CH2Cl2 (3 ꢂ 3 mL), and
the combined organic was washed with deionized water (1 ꢂ 2 mL).
The solvent was removed in vacuo, the residue taken up in CH2Cl2
and filtered through a plug of silica gel, eluting with CH2Cl2 to give
(25), 530 (34), 528 (35), 451 (35), 450 (59), 449 (47), 448 (45), 447
(27), 406 (28), 392 (47), 345 (35), 343 (36), 330 (28), 229 (29); HRMS
(FAB) calcd for C32H48NP56Fe193Ir: 726.2503; found 726.2526.
4.13. (S)-(ꢀ)-2-Di-ortho-tolyl-phosphino-1-
(S)-17 (158 mg, 85%) as an orange solid: mp 128e129 ꢁC; [
a
]
20 ꢀ140
dimethylaminoferrocene iridium(cyclooctadiene) tetrakis[3,5-bis
(trifluoromethyl)phenyl]borate [(S)-19]
D
(c 0.61, CHCl3); 31P NMR (121.5 MHz, CDCl3)
d
14.4; 19F NMR
(282.4 MHz, CDCl3)
d
ꢀ62.34; 1H NMR (300 MHz, CDCl3)
d 7.71 (s,
8H), 7.67e7.56 (m, 5H), 7.53 (s, 4H), 7.48e7.42 (m, 5H), 4.87 (bm,1H),
4.84 (t,1H, J ¼ 2.7 Hz), 4.50 (s, 5H), 4.45 (m,1H), 4.44 (m,1H), 4.31 (m,
1H), 4.04 (bm, 1H), 3.77 (bm, 1H), 3.31e3.15 (m, 3H), 2.60e2.56 (m,
1H), 2.38e2.18 (m, 4H), 2.08e1.83 (m, 7H), 1.73e1.65 (m, 2H); 13C
A solution of [Ir(COD)Cl]2 (29.6 mg, 0.044 mmol) and (S)-9c
(39 mg, 0.088 mmol) in dry CH2Cl2 (2 mL) under argon was heated
at reflux for 1.5 h. After cooling to room temperature, the solution
was concentrated to provide crude (S)-(ꢀ)-2-di-ortho-tolyl-phos-
phino-1-dimethylaminoferrocene iridium(cyclooctadiene) chlo-
NMR (150.9 MHz, CDCl3)
d
161.70 (q, J1311 ¼ 49.8 Hz), 133.3 (d,
CeB
J1331 ¼ 12.1 Hz), 133.0 (d, J1331 ¼ 40.7 Hz), 132.0, 131.8 (d,
ride (67 mg, 99%) as an orange-red solid: mp >230 ꢁC; [
a
]
20 ꢀ49.1
CeP
CeP
D
J1331 ¼ 10.6 Hz),129.7 (d, J1331 ¼ 9.1 Hz),129.2 (d, J1331 ¼ 10.6 Hz),
(c 1.02, CHCl3); FABMS [m/z(%)] 742 (M-Cl, 88), 740 (77), 630 (59),
629 (50), 628 (100); HRMS (FAB) calcd for C34H40NP56Fe193Ir:
742.1877; found 742.1831. To a flask containing the chloride salt
(35 mg, 0.045 mmol) was added NaBArF (50 mg, 0.056 mmol),
CH2Cl2 (1.5 mL) and deionized water (1.5 mL) under argon. The
mixture was stirred for 15 min at room temperature over which
time the color changed from orange to red. The layers were sepa-
rated, the aqueous layer was extracted with CH2Cl2 (3 ꢂ 1.5 mL),
and the combined organic extract was washed with deionized
water (2 mL). The solvent was removed in vacuo and the residue
taken up in CH2Cl2 and filtered through a plug of silica, eluting with
CeP
CeP
CeP
128.9 (q, J1319 ¼ 30.2 Hz),128.8,126.5 (d, J1331 ¼ 58.9 Hz),124.5 (q,
CeF
CeP
J1319
¼
273.1 Hz), 121.6 (d, J1331
¼
22.6 Hz), 117.5, 91.3
CeF
CeP
(d, J1331
¼
7.5 Hz), 90.9 (d, J1331
¼
12.1 Hz), 74.1 (d,
CeP
CeP
J1331 ¼ 6.0 Hz), 72.3, 68.8 (d, J1331 ¼ 96.6 Hz), 66.5, 65.9, 61.1 (d,
CeP
CeP
J1331 ¼ 9.1 Hz), 60.7, 58.64, 57.98, 32.6, 32.4 (d, J1331 ¼ 4.5 Hz), 29.8,
CeP
CeP
28.8, 24.5, 22.2; FABMS [m/z (%)] 740 (M-BArF, 39), 738 (100); HRMS
(FAB) calcd for C34H38NP56Fe193Ir: 740.1720; found 740.1730.
4.12. (S)-(ꢀ)-2-Dicyclohexylphosphino-1-dimethylaminoferrocene
iridium(cyclooctadiene) tetrakis[3,5-bis(trifluoromethyl)phenyl]
borate [(S)-18]
CH2Cl2, to give (S)-19 (58 mg, 81%) as an orange solid: mp
20
161e163 ꢁC; [
a
]
D
ꢀ27.4 (c 0.50, CHCl3); IR (KBr) nmax 3063, 2927,
A solution of [Ir(COD)Cl]2 (22.5 mg, 0.034 mmol) and (S)-9b
(28.5 mg, 0.067 mmol) in dry CH2Cl2 (1.5 mL) under argon were
heated at reflux for 1.5 h. After cooling to room temperature, the
solution was concentrated to provide crude (S)-(ꢀ)-2-dicyclohex-
ylphosphino-1-dimethylaminoferrocene iridium(cyclooctadiene)
chloride (51 mg, 99%) as an orange solid which was used for the
2856,1611,1467, 1355,1279, 1162,1127, 908, 888, 834, 758, 713, 682,
671 cmꢀ1 31P NMR (243 MHz, acetone-d6, e10 ꢁC, 1:1 mixture of
bidentate conformers):
17.6, 12.9; 1H NMR (600 MHz, acetone-
9.31 (dd, 1H,
;
d
d6, e10 ꢁC, 1:1 mixture of bidentate conformers)
d
J131 ¼ 13.2, J11
¼ 7.8 Hz), 9.25 (bs, 1H), 8.57 (bs, 1H), 7.82 (s,
HeP
HeH
2 ꢂ 8H), 7.71 (bs, 1H), 7.71 (s, 2 ꢂ 4H), 7.60 (q, 2H, J11
¼ 7.8 Hz),
HeH
anion exchange without further purification: mp >230 ꢁC;
7.47 (t, 2 ꢂ 1H, J11
¼ 7.2 Hz), 7.45e7.37 (m, 2 ꢂ 2H), 7.33 (t, 1H,
HeH
20
[
a]
ꢀ25.1 (c 0.64, CHCl3); FABMS [m/z (%)] 726 (77, M-Cl), 724
J11
¼ 7.2 Hz), 7.26 (bs, 1H), 7.24 (t, 1H, J11
¼ 7.2 Hz), 7.14 (bs,
D
HeH
HeH
(100), 722 (67), 450 (31), 394 (31), 229 (14); HRMS (FAB) calcd for
C32H48NP56Fe193Ir: 726.2503, found 726.2464. To a flask containing
chloride salt (25 mg, 0.033 mmol) was added NaBArF (36 mg,
0.041 mmol), CH2Cl2 (1 mL), and deionized water (1 mL) under
argon. The mixture was stirred for 15 min at room temperature
resulting in a color change from orange to red. The layers were
separated, the aqueous layer extracted with CH2Cl2 (3 ꢂ1.5 mL), and
the combined organic extract was washed with deionized water
(2 mL). The solvent was removed in vacuo, the residue taken up in
CH2Cl2 and filtered through a plug of silica gel, eluting with CH2Cl2,
to give (S)-18 (46 mg, 88%) as a bright orange solid: mp 159e160 ꢁC;
1H), 5.66 (bs,1H), 5.28 (bs,1H), 5.17 (bs,1H), 5.13 (s,1H), 5.12 (s,1H),
5.08 (s, 1H), 5.04 (s, 1H), 4.81 (bs, 1H), 4.80 (s, 1H), 4.63 (s, 1H), 4.57
(s, 5H), 4.30 (s, 5H), 4.14 (s, 1H), 3.87 (s,1H), 3.72 (s,1H), 3.50 (s, 3H),
3.47 (s, 3H), 3.46 (bs, 1H), 3.07 (s, 3H), 3.00 (s, 3H), 2.63 (bm, 2H),
2.52 (bs, 3H), 2.44e2.38 (bm, 1H), 2.36e2.29 (bm, 2H þ 1H),
2.26e2.19 (bm, 2H), 2.18e2.12 (bm, 1H), 2.04 (s, 3H), 2.02 (bm, 1H),
1.99 (bs, 3H), 1.97 (bm, 1H), 1.92 (s, 3H), 1.84 (bm, 2 ꢂ 1H), 1.77e1.74
(bm, 2H), 1.54e1.52 (bm, 1H); 13C NMR (150.9 MHz, acetone-d6,
e10 ꢁC, 1:1 mixture of bidentate conformers)
d 162.4 (q,
J1311 ¼ 49.8 Hz), 142.4 (d, J1331 ¼ 9.1 Hz),142.2 (d, J1331 ¼ 4.5 Hz),
CeB
CeP
CeP
140.5 (bd, J1331 ¼ 12.1 Hz), 139.4 (bd, J1331 ¼ 22.6 Hz), 137.2 (bd,
CeP
CeP
[
a]
20 ꢀ4.2 (c 0.53, CHCl3); IR (KBr) nmax 3036, 2929, 2857,1641,1634,
J1331 ¼ 21.1 Hz), 136.0 (bd, J1331 ¼ 13.6 Hz), 135.4, 133.6 (d,
D
CeP
CeP
1612, 1464, 1454, 1355, 1278, 1162, 1127, 888, 839, 760, 713, 682,
J1331 ¼ 9.1 Hz), 133.3 (d, J1331 ¼ 7.5 Hz), 133.1 (d, J1331 ¼ 7.5 Hz),
CeP
CeP
CeP
670 cmꢀ1
CDCl3)
;
31P NMR (121.5 MHz, CDCl3)
d
18.6; 19F NMR (282.4 MHz,
7.71 (s, 8H), 7.53 (s, 4H),
133.0 (d, J1331 ¼ 1.5 Hz), 132.7 (d, J1331 ¼ 6.0 Hz), 132,6 (d,
CeP
CeP
d
ꢀ62.32; 1H NMR (600 MHz, CDCl3)
d
J1331 ¼ 1.5 Hz), 132.5 (d, J1331 ¼ 6.0 Hz), 131.6, 130.7 (d,
CeP
CeP
4.90 (bm,1H), 4.84 (t,1H, J ¼ 3.0 Hz), 4.39 (s, 6H), 4.29 (bm,1H), 4.23
(bm, 1H), 4.13 (d, 1H, J ¼ 2.4 Hz), 3.75 (bm, 1H), 3.07 (s, 3H), 2.83 (s,
3H), 2.54 (bm, 1H), 2.41e2.11 (m, 5H), 2.05e2.01 (m, 4H), 1.95 (m,
1H), 1.87e1.68 (m, 12H), 1.62e1.56 (m, 1H), 1.45e1.34 (m, 3H),
J1331
¼
48.3 Hz), 129.8 (qq, J1319
13.6 Hz), 127.1 (d, J13C3e1P
¼
31.7, 3.0 Hz), 128.3
CeP
CeF
(d, J1331 ¼ 58.9 Hz), 127.4 (d, J1331 ¼ 15.1 Hz), 127.2 (d,
CeP
J1331
¼
¼
10.6 Hz), 126.5
CeP
CeP
(d, J1331 ¼ 27.2 Hz), 125.7 (d, J1331 ¼ 24.1 Hz), 125.2 (q,
CeP
CeP
1.25e1.18 (m, 4H); 13C NMR (150.9 MHz, CDCl3)
d
161.7 (q,
J1319 ¼ 271.6 Hz), 118.3 (sept, J1319 ¼ 4.5 Hz), 93.8 (bs), 92.1 (d,
CeF
CeF
J1311 ¼ 49.8 Hz), 134.8, 128.9 (q, J1319 ¼ 27.1 Hz), 125.7 (d,
J1331
CeP
¼
12.1 Hz), 91.6 (bs), 89.1 (bs), 75.8 (bs), 74.5
CeB
CeF
J1331 ¼ 22.6 Hz), 124.5 (q, J1319 ¼ 273 Hz), 117.5, 91.8 (d,
(d, J1331 ¼ 6.0 Hz), 73.2, 72.7, 72.5 (d, J1331 ¼ 19.6 Hz), 71.9 (d,
CeP
CeF
CeP
CeP
J1331 ¼ 10.6 Hz), 88.8 (d, J1331 ¼ 12.1 Hz), 74.8 (d, J1331 ¼ 4.5 Hz),
J1331
CeP
¼
22.6 Hz), 68.2, 65.8, 63.8 (bs), 61.8 (bs), 60.7 (d,
CeP
CeP
CeP
71.3, 70.1 (d, J1331 ¼ 45.3 Hz), 67.6, 59.3, 58.1 (d, J1331 ¼ 9.1 Hz),
J1331 ¼ 10.6 Hz), 60.2 (d, J1331 ¼ 9.1 Hz), 60.1 (bs), 59.1 (bs), 57.9,
CeP
CeP
CeP
CeP
57.9, 57.1, 52.3, 39.3 (d, J1331 ¼ 25.7 Hz), 38.6, (d, J1331 ¼ 30.2 Hz),
57.8, 53.0, 51.1, 34.2, 33.9 (bs), 32.0 (bs), 31.5, 31.3, 31.1 (bs), 29.1
CeP
CeP
33.6 (d, J1331 ¼ 3.0 Hz), 32.0 (d, J1331 ¼ 3.0 Hz), 31.0, 30.6, 29.8 (d,
(bs), 28.4, 23.3 (2 ꢂ d, J1331 ¼ 4.5 Hz), 22.3 (bd, J1331 ¼ 3.0 Hz),
CeP
CeP
CeP
CeP
J1331 ¼ 6.0 Hz), 29.6, 28.8, 27.9, 27.3 (d, J1331 ¼ 9.1 Hz), 27.1 (d,
21.9 (d, J1331 ¼ 3.0 Hz); FABMS [m/z (%)] 742 (62, M-BArF), 740 (61),
CeP
CeP
CeP
J1331 ¼ 13.5 Hz), 27.1 (d, J1331 ¼ 10.6 Hz), 27.1, 27.0 (d,
630 (54), 629 (49), 628 (100); HRMS (FAB) calcd for
C34H40NP56Fe193Ir 742.1876, found 742.1915; Anal. calcd for
C66H52NP56Fe193IrBF24: C, 49.39; H, 3.27. Found: C, 48.74; H, 3.25.
CeP
CeP
J1331 ¼ 10.6 Hz), 25.7, 25.4; FABMS [m/z (%)] 726 (58, M-BArF), 725
CeP
(41) 724 (100), 723 (41), 722 (89), 721 (29), 720 (48), 612 (25), 610