Organometallics
Article
H 3.95, S 1.87. Found: C 47.68, H 3.92, S 1.84. MS HR-ESI [found
847.2773, C36H55IrO3PSSi2 (M − BArF)+ requires 847.2777].
[Ir(cod)(L1d)]BArF (6). Yield: 119 mg (93%). 31P NMR (CDCl3),
tBu), 31.8 (b, CH2, COD), 32.3 (CH3, tBu), 33.7 (b, CH2, COD), 34.8
(b, CH2), 34.9 (C, tBu), 35.0 (C, tBu), 50.9 (d, JC−P = 5.44 Hz, CH,
COD), 66.9 (CH−S), 76.9 (CH−O), 82.1 (b, CH, COD), 102.4
(d, JC−P = 15.6 Hz, CH, COD), 104.0 (d, JC−P = 14.82 Hz, CH,
COD), 117.4 (b, CH, BArF), 120.4−134.1 (aromatic carbons),
134.8 (b, CH, BArF), 135.7−144.9 (aromatic carbons), 161.7 (q,
1JC−B = 49.0 Hz, C−B, BArF). Anal. Calcd (%) for C78H75BF24IrO3PS:
C 52.56, H 4.24, S 1.80. Found: C 52.34, H 4.22, S 1.77. MS HR-ESI
[found 919.3858, C46H63IrO3PS (M − BArF)+ requires 919.3865].
[Ir(cod)(L2e)]BArF (10). Yield: 122 mg (93%). 31P NMR (C6D6),
1
δ: 99.8. H NMR (CDCl3), δ: 1.38 (b, 2H, CH2), 1.44 (s, 9H, CH3,
t
tBu), 1.53 (s, 9H, CH3, Bu), 1.56 (m, 2H, CH2), 1.57 (s, 9H, CH3,
tBu), 1.64 (s, 3H, CH3), 1.75 (b, 6H, CH2), 1.84 (s, 3H, CH3), 2.1−
2.2 (b, 6H, CH2), 2.23 (s, 3H, CH3), 2.25 (s, 3H, CH3), 2.69 (m, 1H,
CH-S), 4.24 (m, 1H, CH, COD), 4.36 (m, 1H, CH, COD), 4.91
(m, 2H, CH, COD and CH−O), 5.59 (m, 1H, CH, COD),
7.17−7.70 (m, 14H, CH, Ar). 13C NMR (CDCl3), δ: 16.4 (CH3−
Ph), 16.7 (CH3−Ph), 20.3 (CH3−Ph), 20.6 (CH3−Ph), 23.7 (CH2),
1
t
δ: 88.8. H NMR (C6D6), δ: 1.38 (s, 9H, CH3, Bu), 1.55 (m, 2H,
t
t
25.8 (CH2), 27.8 (b, CH2), 29.2 (CH2), 31.2 (CH3, Bu), 31.2 (b,
CH2, COD), 1.57 (s, 9H, CH3, Bu), 1.66 (s, 3H, CH3), 1.72 (b, 2H,
t
t
CH2), 31.7 (CH3, Bu), 31.9 (CH3, Bu), 33.2 (b, CH2), 34.7 (b,
CH2), 1.75 (s, 3H, CH3), 1.81 (m, 2H, CH2, COD), 1.90−2.03 (m,
6H, CH2), 2.10 (m, 2H, CH2, COD), 2.17 (s, 3H, CH3−Ph), 2.20 (s,
3H, CH3−Ph), 2.25 (m, 2H, CH2, COD), 2.42 (s, 3H, CH3), 2.68 (m,
1H, CH−S), 2.88 (s, 3H, CH3), 3.25 (m, 1H, CH, COD), 3.81 (m,
1H, CH, COD), 4.32 (m, 1H, CH, COD), 4.46 (m, 1H, CH−
O), 4.86 (m, 1H, CH, COD), 7.07−7.64 (m, 17H, CH, Ar). 13C
NMR (C6D6), δ: 16.4 (CH3), 16.6 (CH3), 20.3 (CH3−Ph), 20.4
(CH3−Ph), 22.6 (CH3), 22.8 (CH3), 25.4 (CH2), 26.5 (b, CH2,
COD), 29.7 (CH2), 29.9 (CH2), 30.3 (CH2), 31.4 (b, CH2, COD),
31.7 (CH3, tBu), 32.8 (CH3, tBu), 34.2 (b, CH2, COD), 34.6 (b, CH2,
COD), 34.8 (C, tBu), 35.3 (C, tBu), 52.6 (CH, COD), 66.2 (CH−
S), 76.2 (CH−O), 78.3 (b, CH, COD), 102.3 (d, JC−P = 14.11 Hz,
CH, COD), 105.3 (d, JC−P = 16.43 Hz, CH, COD), 117.5 (b,
CH, BArF), 120.4−134.4 (aromatic carbons), 134.8 (b, CH,
t
t
t
CH2), 35.2 (C, Bu), 35.3 (C, Bu), 35.5 (C, Bu), 47.7 (CH-S), 57.6
(C, StBu), 74.1 (b, CH, COD), 77.7 (b, CH, COD), 81.6 (CH−
O), 99.2 (d, JC−P = 19.7 Hz, CH, COD), 110.4 (d, JC−P = 14.0 Hz,
CH, COD), 117.6 (b, CH, BArF), 123.3−134.4 (aromatic
carbons), 134.9 (b, CH, BArF), 135.9−143.9 (aromatic carbons),
1
161.9 (q, JC−B = 49.4 Hz, C−B, BArF). Anal. Calcd (%) for
C74H75BF24IrO3PS: C 51.25, H 4.36, S 1.85. Found: C 51.05, H 4.34, S
1.82. MS HR-ESI [found 871.3861, C42H63IrO3PS (M − BArF)+
requires 871.3865].
[Ir(cod)(L1e)]BArF (7). Yield: 118 mg (92%). 31P NMR (C6D6), δ:
1
94.6. H NMR (CDCl3), δ: 1.4−1.6 (b, 4H, CH2), 1.40 (s, 9H, CH3,
tBu), 1.56 (s, 9H, CH3, Bu), 1.6−1.9 (m, 6H, CH2), 1.62 (s, 3H,
t
t
CH3), 1.64 (s, 9H, CH3, Bu), 1.85 (s, 3H, CH3), 2.1−2.4 (b, 6H,
1
BArF), 135.4−143.5 (aromatic carbons), 161.5 (q, JC−B = 49.2 Hz,
CH2), 2.25 (s, 3H, CH3), 2.29 (s, 3H, CH3), 2.81 (m, 1H, CH-S), 4.12
(m, 1H, CH, COD), 4.55 (m, 1H, CH, COD), 4.92 (m, 2H,
CH, COD and CH−O), 5.98 (m, 1H, CH, COD), 7.12−7.70
(m, 14H, CH, Ar). 13C NMR (CDCl3), δ: 16.7 (CH3−Ph), 20.2
(CH3−Ph), 20.7 (CH3−Ph), 24.4 (CH2), 25.1 (CH2), 25.8 (b, CH2),
C−B, BArF). Anal. Calcd (%) for C78H75BF24IrO3PS: C 52.56, H 4.24,
S 1.80. Found: C 52.38, H 4.23, S 1.79. MS HR-ESI [found 919.3861,
C46H63IrO3PS (M − BArF)+ requires 919.3865].
[Ir(cod)(L2f)]BArF (11). Yield: 107 mg (91%). 31P NMR (C6D6), δ:
1
t
t
99.0. H NMR (C6D6), δ: 1.27 (b, 2H, CH2), 1.56 (m, 2H, CH2,
30.1 (CH2), 30.8 (CH3, Bu), 31.6 (b, CH2), 32.0 (CH3, Bu), 32.2
t
COD), 1.68 (b, 2H, CH2), 1.83 (m, 2H, CH2, COD), 1.91 (m, 2H,
CH2, COD), 2.08 (m, 2H, CH2, COD), 2.36 (m, 4H, CH2), 2.63 (s,
3H, CH3−Ph), 3.05 (s, 3H, CH3−Ph), 3.12 (b, 1H, CH, COD),
3.43 (m, 2H, CH-S, CH, COD), 3.70 (b, 2H, CH−O, CH,
COD) 5.01 (b, 1H, CH, COD), 7.17−8.03 (m, 25H, CH, Ar).
13C NMR (C6D6), δ: 22.8 (CH3−Ph), 23.5 (CH3−Ph), 25.4 (CH2),
27.5 (b, CH2, COD), 29.7 (b, CH2), 30.2 (CH2), 30.3 (CH2), 31.2 (b,
CH2, COD), 33.0 (b, CH2, COD), 35.0 (b, CH2, COD), 51.3 (CH,
COD), 67.4 (CH-S), 75.9 (CH−O), 77.8 (CH, COD), 94.1 (d,
JC−P = 9.37 Hz, CH, COD), 98.5 (d, JC−P = 13.20 Hz, CH,
COD), 117.5 (b, CH, BArF), 120.4−133.9 (aromatic carbons),
134.8 (b, CH, BArF), 134.9−143.2 (aromatic carbons), 161.5 (q,
1JC−B = 49.4 Hz, C−B, BArF). Anal. Calcd (%) for C66H53BF24IrOPS:
C 50.04, H 3.37, S 2.02. Found: C 49.98, H 3.35, S 1.98. MS HR-ESI
[found 721.2240, C34H41IrOPS (M − BArF)+ requires 721.2245].
[Ir(cod)(L2g)]BArF (12). Yield: 112 mg (94%). 31P NMR (C6D6),
δ: 101.6. 1H NMR (C6D6), δ: 1.40 (m, 2H, CH2), 1.50 (m, 2H, CH2),
1.61 (m, 2H, CH2), 1.79−2.01 (m, 6H, CH2 and CH2, COD), 2.08 (s,
3H, CH3), 2.17 (m, 4H, CH2, COD), 2.41 (s, 3H, CH3), 2.56 (b, 1H,
CH, COD), 2.82 (s, 3H, CH3−Ph), 2.90 (s, 3H, CH3−Ph), 3.08 (b,
1H, CH-S), 3.47 (m, 1H, CH, COD), 3.66 (m, 2H, CH−O, CH,
COD), 4.70 (b, 1H, CH, COD), 6.62−8.95 (m, 23H, CH, Ar).
13C NMR (C6D6), δ: 21.7 (d, JC−P = 3.0 Hz, CH3), 22.5 (d, JC−P = 7.0
Hz, CH3−Ph), 22.7 (d, JC−P = 3.0 Hz, CH3−Ph), 23.4 (b, CH3), 25.5
(CH2), 27.8 (b, CH2, COD), 29.6 (CH2), 29.7 (CH2), 30.3 (CH2),
31.2 (CH2, COD), 33.0 (, CH2, COD), 35.7 (d, JC−P = 7.0 Hz, CH2,
COD), 50.8 (CH, COD), 68.0 (CH-S), 76.5 (CH−O), 78.8 (b,
(CH3, Bu), 33.7 (b, CH2), 34.2 (b, CH2), 34.7 (b, CH2), 35.2 (C,
tBu), 36.4 (C, Bu), 46.8 (CH-S), 57.9 (C, StBu), 61.9 (b, CH,
t
COD), 63.4 (b, CH, COD), 79.6 (CH−O), 97.6 (d, JC−P= 18.4 Hz,
CH, COD), 110.2 (d, JC−P = 16.1 Hz, CH, COD), 117.7 (b,
CH, BArF), 120.6−134.6 (aromatic carbons), 134.9 (b, CH,
1
BArF), 137.2−144.2 (aromatic carbons), 161.8 (q, JC−B = 49.4 Hz,
C−B, BArF). Anal. Calcd (%) for C74H75BF24IrO3PS: C 51.25, H 4.36,
S 1.85. Found: C 51.11, H 4.35, S 1.82. MS HR-ESI [found 871.3863,
C42H63IrO3PS (M − BArF)+ requires 871.3865].
[Ir(cod)(L1f)]BArF (8). Yield: 103 mg (91%). 31P NMR (C6D6), δ:
1
100.9. H NMR (C6D6), δ: 1.24 (s, 9H, CH3, StBu), 1.37 (m, 2H,
CH2), 1.49 (m, 2H, CH2), 1.79 (m, 2H, CH2, COD), 1.86 (m, 2H,
CH2), 2.03 (m, 2H, CH2, COD), 2.17 (m, 2H, CH2, COD), 2.28 (m,
2H, CH2, COD), 2.37 (m, 2H, CH2), 2.76 (m, 1H, CH−S), 3.37 (b,
1H, CH−O), 4.20 (m, 2H, CH, COD), 4.81 (m, 1H, CH,
COD), 5.48 (b, 1H, CH, COD), 7.16−7.70 (m, 22H, CH, Ar).
13C NMR (C6D6), δ: 24.3 (CH2), 25.9 (CH2), 28.0 (CH2, COD), 31.3
(CH3, StBu), 31.8 (CH2), 34.0 (CH2, COD), 35.0 (CH2, COD), 35.4
(CH2), 48.7 (CH-S), 59.4 (C, StBu), 74.7 (CH, COD), 77.4 (CH−
O), 83.3 (CH, COD), 96.1 (d, JC−P= 13.31 Hz, CH, COD),
104.8 (d, JC−P = 11.79 Hz, CH, COD), 117.6 (b, CH, BArF),
120.7−134.7 (aromatic carbons), 134.9 (b, CH, BArF), 135.3 (C),
1
161.9 (q, JC−B = 49.2 Hz, C−B, BArF). Anal. Calcd (%) for
C62H53BF24IrOPS: C 48.48, H 3.48, S 2.09. Found: C 48.21, H 3.46, S
2.02. MS HR-ESI [found 673.2239, C30H41IrOPS (M − BArF)+
requires 673.2245].
[Ir(cod)(L2d)]BArF (9). Yield: 125 mg (95%). 31P NMR (C6D6), δ:
88.7. 1H NMR (C6D6), δ: 1.15 (m, 1H, CH2), 1.27 (b, 1H, CH2), 1.47
CH, COD), 96.9 (d, JC−P = 9.4 Hz, CH, COD), 98.1 (d, JC−P
=
t
t
(s, 9H, CH3, Bu), 1.62 (m, 1H, CH2), 1.64 (s, 9H, CH3, Bu), 1.74
(m, 2H, CH2), 1.76 (s, 6H, CH3), 1.84 (m, 3H, CH2), 1.97 (m, 4H,
CH2 and CH2, COD), 2.01 (m, 4H, CH2 and CH2, COD), 2.26 (s,
3H, CH3), 2.27 (s, 3H, CH3), 2.70 (s, 3H, CH3), 2.72 (s, 3H, CH3),
3.26 (b, 1H, CH−S), 3.53 (m, 1H, CH, COD), 4.40 (m, 1H, CH,
COD), 4.54 (m, 2H, CH, COD), 4.74 (m, 1H, CH−O), 7.20−7.71
(m, 17H, CH, Ar). 13C NMR (C6D6), δ: 16.6 (CH3), 16.6 (CH3),
20.3 (CH3−Ph), 20.3 (CH3−Ph), 23.6 (CH3), 23.8 (CH3), 25.4
(CH2), 27.6 (b, CH2, COD), 29.3 (CH2), 29.7 (CH2), 31.6 (CH3,
13.3 Hz, CH, COD), 117.5 (b, CH, BArF), 120.5−133.9
(aromatic carbons), 134.8 (b, CH, BArF), 139.9−143.4 (aromatic
carbons), 161.5 (q, 1JC−B = 49.2 Hz, C−B, BArF). Anal. Calcd (%) for
C68H57BF24IrOPS: C 50.66, H 3.56, S 1.99. Found: C 50.34, H 3.53, S
1.93. MS HR-ESI [found 749.2553, C36H45IrOPS (M − BArF)+
requires 749.2558].
In Situ Preparation of [Ir(H)2(cod)(L1,L2a−g)]BArF. In a typical
experiment hydrogen was bubbled through a CD2Cl2 solution of the
desired [Ir(cod)(P−S)]BArF catalyst precursor (6.2 mmol) to the
K
Organometallics XXXX, XXX, XXX−XXX