Organometallics
Article
132.8, 133.7, 137.5, 138.9, 145.4, 208.1. HRMS (FABMS): calcd for
[C55H47N4O2Co+H]+, m/z 855.3104; found, m/z 855.3091. IR (KBr,
cm−1): ν(CO) 1733 (s), 1717 (s).
hexanone (182 μL) and acetone (318 μL). The reaction mixture was
degassed three times by freeze−thaw−pump cycles, purged with N2,
and photolyzed at 6−10 °C under nitrogen for 8 h. The crude solution
was collected by vacuum distillation and was analyzed by GC/MS. 2-
Heptanone and 2-hept-6-enone were obtained in 129% and 29%
yields, respectively, using naphthalene as the internal standard.
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap),
PPh3 (0.5 equiv), and H2O (500 equiv) in MeCN for 8 h.
Co(tap) (1.0 mg, 0.0013 mmol), PPh3 (0.15 mg, 5.7 × 10−4 mmol),
and H2O (11 μL, 0.611 mmol) were dissolved in 2,6-dimethylcyclo-
hexanone (182 μL) and MeCN (318 μL). The reaction mixture was
degassed three times by freeze−thaw−pump cycles, purged with N2,
and photolyzed at 6−10 °C under nitrogen for 8 h. The crude solution
was collected by vacuum distillation and was analyzed by GC/MS. 2-
Heptanone and 2-hept-6-enone were obtained in 17% and 10% yields,
respectively, using naphthalene as the internal standard.
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap),
PPh3 (0.5 equiv), and H2O (500 equiv) in DMF for 8 h. Co(tap)
(1.0 mg, 0.0013 mmol), PPh3 (0.15 mg, 5.7 × 10−4 mmol), and H2O
(11 μL, 0.611 mmol) were dissolved in 2,6-dimethylcyclohexanone
(182 μL) and DMF (318 μL). The reaction mixture was degassed
three times by freeze−thaw−pump cycles, purged with N2, and
photolyzed at 6−10 °C under nitrogen for 8 h. The crude solution was
collected by vacuum distillation and was analyzed by GC/MS. 2-
Heptanone and 2-hept-6-enone were obtained in 17% and 15% yields,
respectively, using naphthalene as the internal standard.
Reaction of Co(ttp) and Diisopropyl Ketone (10 equiv) with
0.1 equiv of PPh3 and 50 equiv of H2O at 25 °C (Acetone).
Co(ttp) (0.0137 mmol), PPh3 (0.36 mg, 1.37 × 10−3 mmol),
diisopropyl ketone (19.5 μL), and H2O (12 μL) were added to
acetone. The reaction mixture was degassed with three freeze−thaw−
pump cycles and was then stirred at 25 °C in the dark under nitrogen
for 2 h. Excess solvent was removed, and the dark red crude product
was then purified by column chromatography to give a reddish purple
solid of Co(ttp)COiPr (1a; 8.6 mg, 0.0107 mmol, 78% yield).
Reaction of Co(tap) and Diisopropyl Ketone (10 equiv) with
0.1 equiv of PPh3 and 50 equiv of H2O at 25 °C (Acetone).
Co(tap) (0.0126 mmol), PPh3 (0.33 mg, 1.26 × 10−3 mmol),
diisopropyl ketone (17.9 μL), and H2O (11 μL) were added to
acetone. The reaction mixture was degassed with three freeze−thaw−
pump cycles and was then stirred at 25 °C in the dark under nitrogen
for 1.5 h. Excess solvent was removed, and the dark red crude product
was then purified by column chromatography to give the reddish
purple solid Co(tap)COiPr (1b; 9.7 mg, 0.0112 mmol, 89% yield). 1H
NMR (400 MHz, CDCl3): δ −2.80 (sept, 1 H, J = 6.8 Hz), −1.96 (d,
6 H, J = 6.8 Hz), 4.07 (s, 12 H), 7.22 (br. s, 8 H), 8.00 (br. s, 8 H),
8.85 (s, 8 H). 13C NMR (CDCl3, 100 MHz): δ 16.7, 41.9, 55.7, 112.4,
120.9, 132.7, 134.3, 134.8, 145.8, 159.4. HRMS (FABMS): calcd for
[C52H43N4O5Co + H]+, m/z 863.2638; found, m/z 863.2654. IR (KBr,
cm−1): ν(CO) 1750 (s).
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap), H2O
(500 equiv), and PPh3 (0.5 equiv) at 6−10 °C for 8 h. Co(tap)
(1.0 mg, 0.0013 mmol), H2O (11 μL, 0.611 mmol), and PPh3 (0.15
mg, 5.7 × 10−4 mmol) were dissolved in 2,6-dimethylcyclohexanone
(500 μL). The reaction mixture was degassed three times by freeze−
thaw−pump cycles, purged with N2, and photolyzed at 6−10 °C under
nitrogen for 8 h. The crude solution was collected by vacuum
distillation and was analyzed by GC/MS. 2-Heptanone and 2-hept-6-
enone were obtained in 5.7 and 3.6 turnovers, respectively, using
naphthalene as the internal standard.
Reaction of Co(tpclp) and Diisopropyl Ketone (10 equiv)
with 0.1 equiv of PPh3 and 50 equiv of H2O at 25 °C (Acetone).
Co(tpclp) (0.0124 mmol), PPh3 (0.32 mg, 1.22 × 10−3 mmol),
diisopropyl ketone (17.5 μL), and H2O (11 μL) were added to
acetone. The reaction mixture was degassed with three freeze−thaw−
pump cycles and was then stirred at 25 °C in the dark under nitrogen
for 3 h. Excess solvent was removed, and the dark red crude product
was then purified by column chromatography to give the reddish
purple solid Co(tpclp)COiPr (1c; 3.5 mg, 0.0040 mmol, 32% yield).
1H NMR (400 MHz, CDCl3): δ −2.85 (sept, 1 H, J = 6.8 Hz), −1.97
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap), H2O
(500 equiv), PPh3 (0.5 equiv), and iPrOH (20 equiv) at 6−10 °C
for 8 h. Co(tap) (1.0 mg, 0.0013 mmol), H2O (11 μL, 0.611 mmol),
(d, 6 H, J = 6.8 Hz), 7.71 (d, 8 H, J = 8.0 Hz), 8.03 (br. s, 8 H), 8.82
(s, 8 H). 13C NMR (CDCl3, 100 MHz): δ 16.7, 41.9, 120.1, 127.3,
132.9, 134.4, 134.8, 140.1, 145.3. HRMS (FABMS): calcd for
[C48H31N4Cl4OCo + H]+, m/z 881.0627; found, m/z 881.0598. IR
(KBr, cm−1): ν(CO) 1754 (s).
i
PPh3 (0.15 mg, 5.7 × 10−4 mmol), and PrOH (2.0 μL, 0.026 mmol)
were dissolved in 2,6-dimethylcyclohexanone (500 μL). The reaction
mixture was degassed three times by freeze−thaw−pump cycles,
purged with N2, and photolyzed at 6−10 °C under nitrogen for 8 h.
The crude solution was collected by vacuum distillation and was
analyzed by GC/MS. 2-Heptanone and 2-hept-6-enone were obtained
in 10 and 0.9 turnovers, respectively, using naphthalene as the internal
standard.
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap),
PPh3 (0.5 equiv), and H2O (500 equiv) in THF for 8 h. Co(tap)
(1.0 mg, 0.0013 mmol), PPh3 (0.15 mg, 5.7 × 10−4 mmol), H2O (11
μL, 0.611 mmol), and 2,6-dimethylcyclohexanone (182 μL) were
dissolved in THF (308 μL). The reaction mixture was degassed three
times by freeze−thaw−pump cycles, purged with N2, and photolyzed
at 6−10 °C under nitrogen for 8 h. The crude solution was collected
by vacuum distillation and was analyzed by GC/MS. 2-Heptanone and
2-hept-6-enone were obtained in 106% and 40% yields, respectively,
using naphthalene as the internal standard. Data for 2-heptanone: tR =
7.203 min; EIMS m/z (rel %) 114 (1), 99 (1), 85 (1), 71 (2), 59 (1),
58 (6), 43 (10), 41 (1). Data for 2-hept-6-enone: tR = 7.065 min;
EIMS m/z (rel %) 112 (1), 97 (1), 71 (1), 58 (3), 55 (2), 43 (10), 41
(2).
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap), H2O
(500 equiv), PPh3 (0.5 equiv), and iPrOH (50 equiv) at 6−10 °C
for 8 h. Co(tap) (1.0 mg, 0.0013 mmol), H2O (11 μL, 0.611 mmol),
i
PPh3 (0.15 mg, 5.7 × 10−4 mmol), and PrOH (5.0 μL, 0.065 mmol)
were dissolved in 2,6-dimethylcyclohexanone (500 μL). The reaction
mixture was degassed three times by freeze−thaw−pump cycles,
purged with N2, and photolyzed at 6−10 °C under nitrogen for 8 h.
The crude solution was collected by vacuum distillation and was
analyzed by GC/MS. 2-Heptanone was obtained in 13.2 turnovers
using naphthalene as the internal standard.
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap),
PPh3 (0.5 equiv), and H2O (500 equiv) in iPrOH for 8 h. Co(tap)
(1.0 mg, 0.0013 mmol), PPh3 (0.15 mg, 5.7 × 10−4 mmol), and H2O
(11 μL, 0.611 mmol) were dissolved in 2,6-dimethylcyclohexanone
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap), H2O
i
(500 equiv), and PrOH (50 equiv) at 6−10 °C for 8 h. Co(tap)
i
(1.0 mg, 0.0013 mmol), H2O (11 μL, 0.611 mmol), and PrOH (5.0
μL, 0.065 mmol) were dissolved in 2,6-dimethylcyclohexanone (500
μL). The reaction mixture was degassed three times by freeze−thaw−
pump cycles, purged with N2, and photolyzed at 6−10 °C under
nitrogen for 8 h. The crude solution was collected by vacuum
distillation and was analyzed by GC/MS. 2-Heptanone was obtained
in 6.5 turnovers using naphthalene as the internal standard.
i
(182 μL) and PrOH (318 μL). The reaction mixture was degassed
three times by freeze−thaw−pump cycles, purged with N2, and
photolyzed at 6−10 °C under nitrogen for 8 h. The crude solution was
collected by vacuum distillation and was analyzed by GC/MS. 2-
Heptanone and 2-hept-6-enone were obtained in 26% and 5% yields,
respectively, using naphthalene as the internal standard.
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap),
PPh3 (0.5 equiv), and H2O (500 equiv) in Acetone for 8 h.
Co(tap) (1.0 mg, 0.0013 mmol), PPh3 (0.15 mg, 5.7 × 10−4 mmol),
and H2O (11 μL, 0.611 mmol) were dissolved in 2,6-dimethylcyclo-
Photolysis of 2,6-Dimethylcyclohexanone with Co(tap), H2O
i
(500 equiv), PPh3 (1 equiv), and PrOH (50 equiv) at 6−10 °C
for 8 h. Co(tap) (1.0 mg, 0.0013 mmol), H2O (11 μL, 0.611 mmol),
i
PPh3 (0.3 mg, 0.0011 mmol), and PrOH (5.0 μL, 0.065 mmol) were
dissolved in 2,6-dimethylcyclohexanone (500 μL). The reaction
F
Organometallics XXXX, XXX, XXX−XXX