Organometallics
Article
The product was washed with diethyl ether (2 × 5 mL). The yellow
supernatant was removed and the powder dried in vacuo to give an
orange-yellow powder. Single crystals suitable for X-ray diffraction
analysis were grown by solvent evaporation (CDCl3) at room
(+): m/z calculated for C21H30ClIrNO, [M + H]+, 540.1632,
538.1616; found 540.1626, 538.1609; [M − Cl]+, 504.1878,
502.1855; found 504.1865, 502.1845. Elemental analysis: calcd (%)
for C21H30ClIrNO: C 46.78, H 5.42, N 2.60; found: C 46.69, H 5.41,
N 2.6. Crystal data [CCDC no. 1413041]: C21H31ClIrNO2 (4 + H2O),
M = 557.12, monoclinic, P21/c, a = 17.3755(4) Å, b = 15.3635(3) Å, c
1
temperature. Yield: 0.0447 g (81%). H NMR (400 MHz, CDCl3):
δ = 8.63 (d, J = 5.7 Hz, 1H, Harom), 7.56 (t, J = 7.7 Hz, 1H, Harom),
7.25 (s, 20H, Harom + CHphenyl), 6.82 (d, J = 7.9 Hz, 1H, Harom), 1.40
(s, 15H, [CH3]5); 13C NMR (100 MHz, CDCl3): δ = 173.2 (Carom),
150.1 (CHpyridine), 136.2 (CHpyridine), 129.6 (CHphenyl), 128.3
(CHphenyl), 127.6 (CHphenyl), 126.8 (CHphenyl), 125.7 (CHphenyl),
124.0 (CHphenyl), 94.6 (C), 84.3 (CCp*), 8.8 (CH3 Cp*); HR ESI-MS
(+): m/z calculated for C28H29ClIrNO, [M − H]+ 622.1476, 620.1460;
found 622.1474, 620.1455; [M − Cl]+ 588.1873, 586.1850; found
588.1866, 586.1848. Elemental analysis: calcd (%) for C28H29ClIrNO:
C 53.96, H 4.69, N 2.25; found: C 53.96, H 4.74, N 2.34. Crystal data
[CCDC no. 1413039]: C30H31Cl7IrNO (Ir2 + 2 CHCl3), M = 861.91,
monoclinic, P21/n, a = 12.3236(2) Å, b = 16.4094(3) Å, c =
= 15.7991(3) Å, β = 90.789(2)°, V = 4217.15(15) Å3, Z = 8, dcalc
=
1.755 g/cm3, T = 150 K, 18 642 reflections collected, 18 642
independent reflections (Rint = 0.0513), final R1 = 0.0559, final wR2
= 0.1496, GoF = 1.056.
[η5(C5Me5)IrIII{2-(2-quinolyl)-2-propanolate-κO,κN}Cl], 5.
[Cp*IrCl2]2 (0.214 mmol, 165 mg), 2-(2-quinolyl)-2-propanol (0.6
mmol, 127 mg), and Na2CO3 (1.8 mmol, 190 mg) were dissolved in
acetone (20 mL). The resulting orange solution was stirred for 3.5 h at
50 °C, after which time the solution had turned yellow. MgSO4 was
added, and after stirring for 10 min the solution was filtered and the
solvent removed in vacuo to afford a brown oil. The product dissolved
in DCM (5 mL), and hexane was added (25 mL). Upon storage at
−20 °C a precipitate formed. The clear orange supernatant was
removed and the solid dried in vacuo to give a dark orange powder.
Single crystals suitable for X-ray diffraction analysis were grown by
solvent evaporation (DCM) at room temperature. Yield: 78.9 mg
16.4100(3) Å, β = 92.2863(11)°, V = 3315.84(10) Å3, Z = 4, dcalc
=
1.727 g/cm3, T = 150 K, 66 209 reflections collected, 7585
independent reflections (Rint = 0.1312), final R1 = 0.0422, final wR2
= 0.0898, GoF = 1.010.
[η5(C5Me5)IrIII{2,2,4,4-tetramethyl-3-(2-pyridyl)-3-pentano-
late-κO,κN}] hexafluoroantimonate, 3. [Cp*IrCl2]2 (0.1 mmol,
79.8 mg), 2,2,4,4-tetramethyl-3-(2-pyridyl)-3-pentanol, (0.22 mmol,
48.7 mg), and Na2CO3 (0.8 mmol, 84.8 mg) were dissolved in acetone
(20 mL). The resulting orange solution was stirred for 20 h at 50 °C,
without observing any color changes. AgSbF6 (0.22 mmol, 0.0756 g)
and acetonitrile were therefore added (2 mL), and the mixture stirred
for a further 23 h, after which time the solution had turned yellow and
a fine, colorless solid was observed. The solution was filtered through a
0.2 μm Teflon syringe filter and the solvent removed in vacuo. The
resulting red-brown residue was dissolved in dichloromethane (2 mL)
and diethyl ether (30 mL) added, causing the precipitation of a red
solid. The supernatant was removed and the product dried to afford a
fine dark red powder. Single crystals suitable for X-ray diffraction
analysis were grown by diffusion of hexane into a DCM solution at
room temperature. Yield: 0.036 g (46%). 1H NMR (400 MHz,
CDCl3): δ = 9.15 (d, J = 5.9 Hz, 1H, Harom), 8.00 (d, J = 8.26 Hz, 1H,
Harom), 7.91 (t, J = 7.4 Hz, 1H, Harom), 7.65 (t, J = 6.7 Hz, 1H, Harom),
1.88 (s, 15H, [CH3]5), 1.90 (s, 18H, [CH3]6); 13C NMR (100 MHz,
CDCl3): δ = 178.2 (Cpyridine), 152.4 (CHpyridine), 138.0 (CHpyridine),
125.4 (CHpyridine), 123.4 (CHpyridine), 103.9 (C), 88.9 (CCp*), 41.2
(Ct‑butyl), 28.9 (CH3 t‑butyl), 9.8 (CH3 Cp*); ESI-MS (+): m/z calculated
for C27H45F6IrNOSb, [M − SbF6]+, 548.2500, 546.2476; found
548.2493, 546.2472. Elemental analysis: calcd (%) for
C27H45F6IrNOSb: C 36.79, H 4.76, N 1.79, found: C 36.70, H 4.83,
N 1.77. Crystal data [CCDC no. 1413040]: C24H37F6IrNOSb (3), M
1
(68%). H NMR (400 MHz, CDCl3): δ = 8.51 (d, J = 8.2 Hz, 1H,
Harom), 8.09 (d, J = 8.7 Hz, 1H, Harom), 7.80 (d, J = 7.9 Hz, 1H, Harom),
7.78 (t, J = 7.8 Hz, 1H, Harom), 7.56 (t, J = 7.7 Hz, 1H, Harom), 7.19 (d,
J = 8.5 Hz, 1H, Harom), 1.61 (s, 21H, [CCH3]5 + [CH3]2); 13C NMR
(100 MHz, CDCl3): δ = 179.7 (Cquinoline), 144.6 (Cquinoline) 137.2
(CHquinoline), 132.8 (CHquinoline), 130.5 (CHquinoline), 128.6 (Cquinoline),
127.7 (CHquinoline), 127.0 (CHquinoline), 119.2 (CHquinoline), 86.6 (C),
84.4 (CCp*), 35.2 (CH3), 33.1 (CH3), 9.4 (CH3 Cp*); ESI-MS (+): m/
z calculated for C22H27ClIrNO, [M + H]+, 550.1475, 548.1460; found
550.1470, 548.1453; [M − Cl]+, 514.1722, 512.1699; found 514.1710,
512.1689. Elemental analysis: calcd (%) for C22H27ClIrNO: C 48.12,
H 4.96, N 2.55, found: C 47.89, H 4.96, N 2.59. Crystal data [CCDC
no. 1413043]: C22H29ClIrNO2 (5 + H2O), M = 567.11, monoclinic,
P21, a = 7.8422(3) Å, b = 13.7658(4) Å, c = 10.3658(4) Å, β =
106.632(4)°, V = 1072.22(7) Å3, Z = 2, dcalc = 1.757 g/cm3, T = 150 K,
12 281 reflections collected, 4980 independent reflections (Rint
0.0407), final R1 = 0.0277, final wR2 = 0.0465, GoF = 1.000.
=
[η5 (C5 Me5 )IrI I I {3,3,5,5-tetramethyl-1-(2-pyridyl)-
cyclohexanolate-κO,κN}Cl], 6. [Cp*IrCl2]2 (0.1 mmol, 79.3 mg),
3,3,5,5-tetramethyl-1-(2-pyridyl)cyclohexanol (0.24 mmol, 58.3 mg)
and Na2CO3 (0.8 mmol, 84.8 g) were dissolved in acetone (15 mL).
The resulting orange solution was stirred at 50 °C for 36 h, after which
time the solution had turned yellow. MgSO4 was added, and after
stirring for 10 min the solution was filtered and the solvent removed in
vacuo to afford a brown oil. The product recrystallized from DCM (1
mL) upon addition of diethyl ether (20 mL) to give a light brown
powder. Single crystals suitable for X-ray diffraction analysis were
grown by solvent evaporation (DCM) at room temperature. Yield:
= 783.49, triclinic, P1, a = 10.9884(2) Å, b = 11.9229(2) Å, c =
̅
12.9393(2) Å, α = 113.6957(8)°, β = 114.4785(7)°, γ = 91.0354(7)°,
V = 1377.69(4) Å3, Z = 2, dcalc = 1.889 g/cm3, T = 150 K, 25 636
reflections collected, 7937 independent reflections (Rint = 0.1343),
final R1 = 0.0710, final wR2 = 0.1787, GoF = 1.014.
1
0.0455 mg (76%). H NMR (400 MHz, CDCl3): δ = 8.51 (d, J = 5.2
Hz, 1H, Harom), 7.59 (t, J = 8.0 Hz, 1H, Harom), 7.08 (m, 2H, Harom),
1.83 (m, 6H, Hcyclohexyl), 1.67 (s, 15H, [CCH3]5), 1.45 (s, 6H,
[CH3]2), 0.87 (s, 6H, [CH3]2); 13C NMR (100 MHz, CDCl3): δ =
181.6 (Cpyridine), 148.9 (CHpyridine), 136.2 (CHpyridine), 123.1
(CHpyridine), 122.7 (CHpyridine), 89.1 (C), 83.3 (CCp*), 53.3 (CH2),
52.8 (CH2), 36.9 (CH3), 31.9 (C), 29.1 (CH3), 8.7 (CH3 Cp*); ESI-
MS (+): m/z calculated for C25H37ClIrNO, [M − Cl]+, 558.2476,
560.2500; found 558.2484, 560.2501. Elemental analysis: calcd (%) for
C25H37ClIrNO: C 50.45, H 6.27, N 2.35; found: C 50.41, H 6.14, N,
2.42. Crystal data [CCDC no. 1413044]: C25H37ClIrNO (6), M =
595.20, monoclinic, P21/c, a = 16.6537(5) Å, b = 16.6270(10) Å, c =
9.0691(5) Å, β = 96.446(4)°, V = 2495.4(2) Å3, Z = 4, dcalc = 1.584 g/
cm3, T = 150 K, 10 408 reflections collected, 5604 independent
reflections (Rint = 0.0458), final R1 = 0.0411, final wR2 = 0.0527, GoF
= 0.980.
[η5(C5Me5)IrIII{1-(2-pyridyl)cyclohexanolate-κO,κN}Cl], 4.
[Cp*IrCl2]2 (0.2 mmol, 160 mg), 1-(2-pyridyl)cyclohexanol (0.3
mmol, 62.0 mg), and Na2CO3 (0.8 mmol, 84.8 g) were dissolved in
acetone (20 mL). The resulting orange solution was stirred for 5 h at
50 °C, after which time the solution had turned yellow. MgSO4 was
added, and after stirring for 10 min the solution was filtered and the
solvent removed in vacuo to afford an orange-yellow oil. The product
was washed with diethyl ether (20 mL). The yellow supernatant was
removed and the powder dried in vacuo to give an orange powder.
Single crystals suitable for X-ray diffraction analysis were grown by
diffusion of hexane into a DCM solution at room temperature. Yield:
0.0581 g (54%). 1H NMR (400 MHz, CDCl3): δ = 8.49 (d, J = 5.1 Hz,
1H, Harom), 7.63 (t, J = 7.9 Hz, 1H, Harom), 7.12 (m, 2H, Harom), 1.66
(s, 15H, [CH3]5) 2.06 (m, 2H, CHhexyl), 1.81 (m, 1H, CHhexyl), 1.52
(m, 3H, CHhexyl), 1.38 (m, 2H, CHhexyl), 1.17 (m, 2H, CHhexyl); 13C
NMR (100 MHz, CDCl3): δ = 178.2 (Cpyridine), 149.7 (CHpyridine),
137.1 (CHpyridine), 123.5 (CHpyridine), 122.2 (CHpyridine), 84.6 (C), 83.9
(CCp*), 40.9 (CH2), 26.3 (CH2), 22.1 (CH2), 9.1 (CH3 Cp*); ESI-MS
[η5(C5Me5)IrIII{diphenyl(2-quinolyl)methanolate-κO,κN}Cl], 7.
[Cp*IrCl2]2 (0.1 mmol, 79.3 mg), diphenyl(2-quinolyl)methanol
(0.24 mmol, 74.7 mg), and Na2CO3 (0.8 mmol, 84.8 mg) were
dissolved in acetone (15 mL). The resulting orange solution was
I
Organometallics XXXX, XXX, XXX−XXX