Organometallics
Article
[Cp*Ir(B[h]Q)(NCMe)][BArF24] ([3b][BArF24]) (Scheme 2). This
compound was prepared following the general procedure described
above: 2b (150 mg, 0.277 mmol), Na[BArF24] (245.7 mg, 0.277
mmol), MeCN (7 mL), room temperature, 3 h. After recrystallization
with a mixture of CH2Cl2 and n-pentane the product was washed with
n-pentane and the resulting yellow powder of [3b][BArF24] was
isolated in 93% yield (363 mg). Single crystals were grown by slow
diffusion of a mixture of hexane and benzene into a solution of
[3b][BArF24] in 1,2-dichloroethane. Anal. Calcd for C57H38BF24IrN2·
1/10CH2Cl2: C, 48.35; H, 2.71; N, 1.98. Found: C, 48.56; H, 2.72; N,
CDCl3): δ 156.8 (B[h]Q), 154.4 (B[h]Q), 151.6 (C−H, B[h]Q),
142.1 (B[h]Q), 137.7 (C−H, B[h]Q), 134.2 (B[h]Q), 132.7 (C−H,
B[h]Q), 130.7 (C−H, B[h]Q), 129.9 (C−H, B[h]Q), 127.3 (B[h]Q),
123.9 (C−H, B[h]Q), 123.3 (C−H, B[h]Q), 121.9 (C−H, B[h]Q),
119.0 (Ir−NCMe), 91.1 (Cp-Me5), 9.0 (Cp-Me5), 4.1 (Ir-NCMe).
19F{1H} (282 MHz, 298 K, CDCl3): δ −78.9 (CF3, OTf). HRMS-ESI
(m/z): calcd for C25H26IrN2 ([3b]+) 547.1721, found 547.1655.
HRMS-ESI (m/z): calcd for CF3O3S ([OTf]−) 148.9515, found
148.9530.
[Cp*Ir(B[h]Q)(NCMe)][BArF20] ([3b][BArF20]) (Scheme 2). This
compound was prepared following the general procedure described
above: 2b (200 mg, 0.370 mmol), K[BArF20] (264 mg, 0.368 mmol),
MeCN (7 mL), room temperature, 2 h. After recrystallization from a
mixture of CH2Cl2 and n-pentane the resulting powder was washed
with n-pentane and dried under reduced pressure to afford
[3b][BArF20] as a yellow powder in 86% yield (387 mg). Single
crystals were grown by slow diffusion of hexane into a solution of
[3b][BArF20] in dichloromethane (−30 °C). Anal. Calcd for
C49H26BF20IrN2·CH2Cl2: C, 45.82; H, 2.15; N, 2.14. Found: C,
45.96; H, 1.99; N, 2.38. 1H NMR (400 MHz, 298 K, CD2Cl2): δ 8.91
(dd, 1H, J1 = 5.4 Hz, J2 = 1.3 Hz, H−CN B[h]Q), 8.39 (dd, 1H, J1 =
8.0 Hz, J2 = 1.4 Hz, HAr B[h]Q), 8.02 (dd, 1H, J1 = 6.9 Hz, J2 = 1.3 Hz,
HAr B[h]Q), 7.93 (d, 1H, J = 8.8 Hz, HAr B[h]Q), 7.74 (dd, 1H, J1 =
7.9 Hz, J2 = 1.2 Hz, HAr B[h]Q), 7.72−7.66 (m, 2H, HAr B[h]Q), 7.63
(dd, 1H, J1 = 8.1 Hz, J2 = 5.3 Hz, HAr B[h]Q), 2.15 (s, 3H, Ir-NCMe),
1.75 ppm (s, 15H, Cp-Me5). 13C NMR (126 MHz, 295 K, CD2Cl2): δ
158.0 (C-N, B[h]Q), 154.7 (B[h]Q), 150.6 (H-CN, B[h]Q), 148.9
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1.99. H NMR (500 MHz, 298 K, CD2Cl2): δ 8.89 (dd, 1H, J1 = 5.3
Hz, J2 = 1.2 Hz, H-CN B[h]Q), 8.36 (dd, 1H, J1 = 8.0 Hz, J2 = 1.1
Hz, HAr B[h]Q), 8.01 (dd, 1H, J1 = 6.9 Hz, J2 = 0.9 Hz, HAr B[h]Q),
7.92 (d, 1H, J = 8.7 Hz, HAr B[h]Q), 7.73 (m, 9H, 1HAr in B[h]Q +
8Hortho in BArF24), 7.67−7.70 (m, 2H, HAr B[h]Q), 7.56 (m, 4Hpara in
BArF24), 7.61 (dd, 1H, J1 = 7.9 Hz, J2 = 5.3 Hz, HAr B[h]Q), 2.12 (s,
3H, Ir-NCMe), 1.73 (s, 15H, Cp-Me5). 13C NMR (126 MHz, 298 K,
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CD2Cl2): δ 161.5−162.7 (1:1:1:1 quartet, JC−B = 49.8 Hz, C−B in
BArF24), 157.6 (C-N, B[h]Q), 154.2 (CB[h]Q), 150.2 (H-CN,
B[h]Q), 142.3 (B[h]Q), 138.4 (C−H, B[h]Q), 135.2 (m, C−Hortho in
BArF24), 134.8 (B[h]Q), 133.1 (C−H, B[h]Q), 131.4 (C−H, B[h]Q),
2
3
130.6 (C−H, B[h]Q), 128.9−129.6 (q, JC−F = 31.5 Hz, JC−B = 3.0
Hz, C-CF3 in BArF24), 128.1 (B[h]Q), 125.0 (q, 1JC−F = 272.5 Hz, CF3
in BArF24), 124.1 (C−H, B[h]Q), 122.9 (C−H, B[h]Q), 122.5 (C−H,
B[h]Q), 118.5 (Ir−NCMe), 117.9 (m, C−Hpara in BArF24), 91.6 (Cp-
Me5), 9.1 (Cp-Me5), 4.2 (Ir-NCMe). 19F NMR (282 MHz, 298 K,
CD2Cl2): δ −63.8 (s, CF3 in BArF24). 11B NMR (128 MHz, 298 K,
CD2Cl2): δ −6.6 (bs). HRMS-ESI: calcd for C25H26IrN2 ([3b]+) (m/
z) 547.1721, found 547.1716. HRMS-ESI: calcd for C32H12BF24
([BArF24]−) (m/z) 863.0649, found 863.0656.
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(C-F, d (br), J = 240.0 Hz, 2C of C6F5 in BArF20), 142.7 (B[h]Q),
138.8 (C-F, d (br), 1J = 240.0 Hz, 1C of p-C6F5 in BArF20), 138.8 (C−
H, B[h]Q), 136.2 (C−F, d (br), 1J = 240.0 Hz, 2C of C6F5 in BArF20),
135.3 (B[h]Q), 133.6 (C−H, B[h]Q), 131.8 (C−H, B[h]Q), 131.0
(C−H, B[h]Q), 128.5 (B[h]Q), 124.5 (C−H, B[h]Q), 123.3 (C−H,
B[h]Q), 122.9 (C−H, B[h]Q), 119.0 (Ir−NCMe), 92.1 (Cp-Me5), 9.6
(Cp-Me5), 4.6 (Ir−NCMe), [the 1:1:1:1 quartet characterizing the C-B
bond in C6F5 (BArF20) escaped detection]. 11B NMR (128 MHz, 298
K, CD2Cl2): δ −16.6 (s). HRMS-ESI: calcd for C23H23IrN ([3b -
NCMe]+) (m/z) 506.1455, found 506.1462.
[Cp*Ir(B[h]Q)(NCMe)][BPh4] ([3b][BPh4]) (Scheme 2). This com-
pound was prepared following the general procedure described above:
2b (200 mg, 0.37 mmol), Na[BPh4] (126 mg, 0.37 mmol), MeCN (10
mL), 40 °C, 24 h. After recrystallization from a mixture of CH2Cl2 and
n-pentane the resulting powder was washed with n-pentane and dried
under reduced pressure to afford [3b][BPh4] as a yellow powder in
78% yield (244 mg). Single crystals were grown by slow diffusion of
hexane and benzene into a solution of [3b][BPh4] in 1,2-dichloro-
ethane. Anal. Calcd for C49H46BIrN2·1/3CH2Cl2: C, 66.26; H, 5.26; N,
3.13. Found: C, 66.49; H, 5.24; N, 2.96. 1H (500 MHz, 298 K,
CD2Cl2): δ 8.87 (dd, 1H, J1 = 5.3 Hz, J2 = 1.2 Hz, HAr B[h]Q), 8.31
(dd, 1H, J1 = 8.0 Hz, J2 = 1.1 Hz, HAr B[h]Q), 8.01 (dd, 1H, J1 = 7.1
Hz, J2 = 0.8 Hz, HAr B[h]Q), 7.93 (d, 1H, J = 8.8 Hz, HAr B[h]Q), 7.74
(d, 1H, J = 7.8 Hz, HAr B[h]Q), 7.69 (t, 2H, J = 7.0 Hz, HAr B[h]Q),
7.26 (m, 9H, 1HAr in B[h]Q + 8HAr in BPh4), 6.95 (t, 8H, J = 7.2 Hz,
HAr in BPh4), 6.82 (m, 4H, HAr in BPh4), 1.74 (s, 3H, Ir-NCMe), 1.59
(s, 15H, Cp-Me5). 13C NMR (126 MHz, 298 K, CD2Cl2): δ 164.5
[Cp*Ir(DB[f,h]Q)(NCMe)][BArF24] ([3c][BArF24]) (Scheme 2). This
compound was prepared following the general procedure described
above: 2c (100 mg, 0.169 mmol), Na[BArF24] (150.0 mg, 0.169
mmol), MeCN (10 mL), 50 °C, 5 h. After recrystallization with a
mixture of CH2Cl2 and n-pentane (∼−30 °C) the resulting powder
was washed with n-pentane and dried under reduced pressure to afford
[3c][BArF24] as an orange-yellow powder in 70% yield (172 mg).
Anal. Calcd for C61H40BF24IrN2·4/5CH2Cl2: C, 48.58; H, 2.74; N,
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1.83. Found: C, 48.22; H, 2.70; N, 1.59. H (500 MHz, 298 K, d6-
acetone): δ 9.33 (d, 1H, J = 8.3 Hz, HAr DB[f,h]Q), 9.28 (d, 1H, J =
5.5 Hz, HAr DB[f,h]Q), 8.86 (t, 2H, J = 7.6 Hz, HAr DB[f,h]Q), 8.46
(d, 1H, J = 8.0 Hz, HAr DB[f,h]Q), 8.13 (d, 1H, J = 7.3 Hz, HAr
DB[f,h]Q), 7.85−7.91 (m, 2H, HAr DB[f,h]Q), 7.79 (m; 1HAr in
DB[f,h]Q + 8Hortho in BArF24), 7.73 (t, 1H, J = 7.5 Hz, HAr DB[f,h]Q),
7.68 (m, 4Hpara in BArF24), 2.41 (s, 3H, Ir-NCMe), 1.86 (s, 15H, Cp-
Me5). 13C NMR (126 MHz, 298 K, d6-acetone): δ 162.6 (1:1:1:1
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(1:1:1:1 quartet, JC−B = 49.2 Hz, C−B in BPh4), 157.5 (B[h]Q),
154.3 (B[h]Q), 150.2 (H-C=N, B[h]Q), 142.3 (B[h]Q), 138.5 (H-C,
3
B[h]Q), 136.2 (1:1:1:1 quartet, JC−B = 1.4 Hz, C−Hortho in BPh4),
134.8 (B[h]Q), 133.1 (C−H, B[h]Q), 131.4 (C−H, B[h]Q), 130.6
(C−H, B[h]Q), 128.7 (B[h]Q), 126.0 (1:1:1:1 quartet, 2JC−B = 2.8 Hz,
C−Hmeta in BPh4), 124.2 (C−H, B[h]Q), 123.1 (C−H, B[h]Q), 122.5
(C−H, B[h]Q), 122.1 (s, C−Hpara in BPh4), 119.0 (Ir−NCMe), 91.5
(Cp-Me5), 9.2 (Cp-Me5), 3.4 (Ir-NCMe). 11B (128 MHz, 298 K,
CDCl3): δ −6.5 (m). HRMS-ESI: calcd for C25H26IrN2 ([3b]+) (m/z)
547.1721, found 547.1758. HRMS-ESI: calcd for C24H20B ([BPh4]−)
(m/z) 319.1657, found 319.1655.
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quartet, JC−B = 49.6 Hz, C-B in BArF24), 158.7 (DB[f,h]Q), 156.3
(DB[f,h]Q), 152.4 (H-C=N, DB[f,h]Q), 141.3 (DB[f,h]Q), 135.5
(C−H, DB[f,h]Q), 134.6 (C−H, DB[f,h]Q), 134.6 (C−H, DB[f,h]Q),
133.1 (DB[f,h]Q), 132.2 (m, DB[f,h]Q), 130.4 (C−H, DB[f,h]Q),
130.1 (C−H, DB[f,h]Q), 130.0 (q, 2JC−F = 32.3 Hz, C-CF3 in BArF24),
128.8 (C−H, DB[f,h]Q), 128.7 (DB[f,h]Q), 127.4 (DB[f,h]Q), 125.4
[Cp*Ir(B[h]Q)(NCMe)][OTf] ([3b][OTf]) (Scheme 2). This com-
pound was prepared following the general procedure described above:
2b (93.5 mg, 0.173 mmol), Ag[OTf] (342.2 mg, 0.173 mmol), MeCN
(7 mL), room temperature, 2 h. After the resulting residue was washed
with n-pentane, [3b][OTf] was recovered as a yellow powder in 76%
yield (113 mg). Anal. Calcd for C26H26F3IrN2O3S·1/10CH2Cl2: C,
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(q, JC−F = 271.5 Hz, CF3 in BArF24), 125.0 (C−H, DB[f,h]Q), 124.9
(C−H, DB[f,h]Q), 124.4 (C−H, DB[f,h]Q), 118.4 (m, C−Hpara in
BArF24), 118.3 (Ir−NCMe), 92.3 (Cp-Me5), 10.0 (Cp-Me5), 3.4 (Ir-
NCMe). 19F{1H} NMR (282 MHz, 298 K, d6-acetone): δ −64.2 (s,
CF3 in BArF24). 11B NMR (128 MHz, 298 K, d6-acetone): δ −6.54
(m). HRMS-ESI: calcd for C29H28IrN2 ([3c]+) (m/z) 597.1887, found
597.1914. HRMS-ESI: calcd for C32H12BF24 ([BArF24]−) (m/z)
863.0649, found 863.0649.
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44.51; H, 3.75; N, 3.98. Found: C, 44.81; H, 3.77; N, 4.03. H (400
MHz, 298 K, CDCl3): δ 9.26 (d, 1H, J = 5.3 Hz, H−CN B[h]Q),
8.32 (d, 1H, J = 8.1 Hz, HAr B[h]Q), 7.97 (d, 1H, J = 6.7 Hz, HAr
B[h]Q), 7.87 (d, 1H, J = 8.8 Hz, HAr B[h]Q), 7.77 (dd, 1H, J1 = 8.0
Hz, J2 = 8.0 Hz, HAr B[h]Q), 7.63−7.70 (m, 3H, HAr B[h]Q), 2.28 (s,
3H, Ir-NCMe), 1.79 (s, 15H, Cp-Me5). 13C (126 MHz, 298 K,
Procedure for Piezometric Monitoring of the Catalytic O-
Silylation of Benzyl Alcohol (eq 1, Table 2). Benzyl alcohol (1.0
mL, 9.6 mmol or 0.5 mL, 4.8 mmol) and HSiEt3 (0.8 mL, 5.0 mmol)
O
Organometallics XXXX, XXX, XXX−XXX