Organometallics
Article
raphy on silica gel with a hexane/CH2Cl2 solvent mixture (7/1) as
eluent. The red solid Rh(ttp)(cyclohexyl)23 (3a; 6.2 mg, 0.0072 mmol,
74%) was collected.
150 °C for 10 h. Excess benzene was removed by rotary evaporation.
The residue was purified by pipet column chromatography on silica gel
with a hexane/CH2Cl2 solvent mixture (7/1) as eluent. The red solid
Rh(tmp)Me25 (6a; 7.5 mg, 0.0083 mmol, 86%) was collected.
Reaction of Rh(tmp)Cl with BnBr and KOH in Air at 150 °C.
Rh(tmp)Cl (1b; 8.9 mg, 0.0097 mmol), aqueous KOH (5.5 M, 0.0175
mL, 0.096 mmol), and benzyl bromide (2c; 0.0115 mL, 0.096 mmol)
were added to benzene (2.0 mL). The mixture was heated to 150 °C
for 3 h. Excess benzene was removed by rotary evaporation. The
residue was purified by pipet column chromatography on silica gel
with a hexane/CH2Cl2 solvent mixture (7/1) as eluent. The red solid
Rh(tmp)Bn1b,25b (6b; 4.6 mg, 0.0047 mmol, 49%) was collected.
Reaction of Rh(tmp)Cl with n-BuBr and KOH in Air at 150 °C.
Rh(tmp)Cl (1b; 8.9 mg, 0.0097 mmol), aqueous KOH (5.5 M, 0.0175
mL, 0.096 mmol), and n-butyl bromide (2e; 0.0105 mL, 0.098 mmol)
were added to benzene (2.0 mL). The mixture was heated to 150 °C
for 5 h. Excess benzene was removed by rotary evaporation. The
residue was purified by pipet column chromatography on silica gel
with a hexane/CH2Cl2 solvent mixture (7/1) as eluent. The red solid
Rh(tmp)(n-butyl)2b (6c; 5.4 mg, 0.0057 mmol, 59%) was collected.
Reaction of Rh(ttp)Cl with n-Pentyl Tosylate and KOH in Air.
Rh(ttp)Cl (1a; 11.3 mg, 0.014 mmol), aqueous KOH (5.5 M, 0.026
mL, 0.14 mmol), and n-pentyl tosylate (7; 0.031 mL, 0.14 mmol) were
added to benzene (2.0 mL). The mixture was heated to 120 °C for 1 h.
Excess benzene was removed by rotary evaporation. The residue was
purified by pipet column chromatography on silica gel with a hexane/
CH2Cl2 solvent mixture (7/1) as eluent. The first band was collected
to give the red solid Rh(ttp)(n-pentyl)23 (3b; 5.1 mg, 0.0060 mmol,
43%).
Reaction of Rh(ttp)Cl with Cyclohexyl Iodide and KOH in Air.
Rh(ttp)Cl (1a; 7.8 mg, 0.0097 mmol), aqueous KOH (5.5 M, 0.0175
mL, 0.096 mmol), and cyclohexyl iodide (5a; 0.0125 mL, 0.097 mmol)
were added to benzene (2.0 mL). The mixture was heated to 120 °C
for 24 h. Excess benzene was removed by rotary evaporation. The
residue was purified by pipet column chromatography on silica gel
with a hexane/CH2Cl2 solvent mixture (7/1) as eluent. The red solid
Rh(ttp)(cyclohexyl)23 (3a; 6.2 mg, 0.0072 mmol, 74%) was collected.
Reaction of Rh(ttp)Cl with n-Octyl Chloride and KOH in Air.
Rh(ttp)Cl (1a; 7.7 mg, 0.0095 mmol), aqueous KOH (5.5 M, 0.0175
mL, 0.096 mmol), and n-octyl chloride (4b; 0.0165 mL, 0.097 mmol)
were added to benzene (2.0 mL). The mixture was heated to 120 °C
for 3 h. Excess benzene was removed by rotary evaporation. The
residue was purified by pipet column chromatography on silica gel
with a hexane/CH2Cl2 solvent mixture (7/1) as eluent. The red solid
Rh(ttp)(n-octyl)1d (3c; 6.8 mg, 0.0077 mmol, 81%) was collected.
Reaction of Rh(ttp)Cl with n-Butyl Iodide and KOH in Air.
Rh(ttp)Cl (1a; 7.8 mg, 0.0097 mmol), aqueous KOH (5.5 M, 0.0175
mL, 0.096 mmol), and n-butyl iodide (5b; 0.011 mL, 0.097 mmol)
were added to benzene (2.0 mL). The mixture was heated to 120 °C
for 24 h. Excess benzene was removed by rotary evaporation. The
residue was purified by pipet column chromatography on silica gel
with a hexane/CH2Cl2 solvent mixture (7/1) as eluent. The red solid
Rh(ttp)(n-butyl)8 (3d; 6.1 mg, 0.0074 mmol, 76%) was collected.
Reaction of Rh(ttp)Cl with BnBr and KOH in Air. Rh(ttp)Cl
(1a; 7.8 mg, 0.0097 mmol), aqueous KOH (5.5 M, 0.0175 mL, 0.096
mmol), and benzyl bromide (2c; 0.0115 mL, 0.096 mmol) were added
to benzene (2.0 mL). The mixture was heated to 120 °C for 1 h.
Excess benzene was removed by rotary evaporation. The residue was
purified by pipet column chromatography on silica gel with a hexane/
CH2Cl2 solvent mixture (7/1) as eluent. The red solid Rh(ttp)Bn24
(3e; 5.0 mg, 0.0058 mmol, 60%) was collected.
Reaction of Rh(ttp)Cl with Neopentyl Bromide and KOH in
Air. Rh(ttp)Cl (1a; 7.9 mg, 0.0098 mmol), aqueous KOH (5.5 M,
0.0175 mL, 0.096 mmol), and neopentyl bromide (2d; 0.012 mL,
0.096 mmol) were added to benzene (2.0 mL). The mixture was
heated to 120 °C for 5 h. Excess benzene was removed by rotary
evaporation. The residue was purified by pipet column chromatog-
raphy on silica gel with a hexane/CH2Cl2 solvent mixture (7/1) as
eluent. The red solid Rh(ttp)(neopentyl) (3f; 3.5 mg, 0.0042 mmol,
43%) was collected. Rf = 0.80 (hexane/CH2Cl2 1/1). 1H NMR
(CDCl3, 400 MHz): δ −4.99 (d, 2JRh−H = 2.8 Hz, 2H), −2.49 (s, 9H),
2.69 (s, 12H), 7.53 (t, J = 6.6 Hz, 8H), 7.99 (d, J = 7.5 Hz, 4H), 8.06
(d, J = 7.4 Hz, 4H), 8.70 (s, 8H); 13C NMR (CDCl3, 100 MHz) δ
21.7, 26.1, 32.5 (1JRh−C = 27.0 Hz), 32.5, 122.9, 127.4, 127.5, 131.5,
133.7, 134.1, 137.3, 139.4, 143.7. HRMS (FABMS): calcd for
C53H47N4Rh [M]+ m/z 842.2850, found m/z 842.285632.
Reaction of Rh(ttp)Cl with Methyl Iodide and KOH in Air.
Rh(ttp)Cl (1a; 7.8 mg, 0.0097 mmol), aqueous KOH (5.5 M, 0.0175
mL, 0.096 mmol), and methyl iodide (5c; 0.006 mL, 0.096 mmol)
were added to benzene (2.0 mL). The mixture was heated to 120 °C
for 24 h. Excess benzene was removed by rotary evaporation. The
residue was purified by pipet column chromatography on silica gel
with a hexane/CH2Cl2 solvent mixture (7/1) as eluent. The red solid
Rh(ttp)Me7 (3g; 4.1 mg, 0.0052 mmol, 54%) was collected.
Reaction of Rh(tmp)Cl with Methyl Iodide and KOH in Air at
120 °C. Rh(tmp)Cl (1b; 8.9 mg, 0.0097 mmol), aqueous KOH (5.5
M, 0.0175 mL, 0.096 mmol), and methyl iodide (5c; 0.006 mL, 0.096
mmol) were added to benzene (2.0 mL). The mixture was heated to
120 °C for 84 h. Excess benzene was removed by rotary evaporation.
The residue was purified by pipet column chromatography on silica gel
with a hexane/CH2Cl2 solvent mixture (7/1) as eluent. The red solid
Rh(tmp)Me25 (6a; 4.4 mg, 0.0049 mmol, 51%) was collected.
Reaction of Rh(tmp)Cl with Methyl Iodide and KOH in Air at
150 °C. Rh(tmp)Cl (1b; 8.9 mg, 0.0097 mmol), aqueous KOH (5.5
M, 0.0175 mL, 0.096 mmol), and methyl iodide (5c; 0.006 mL, 0.096
mmol) were added to benzene (2.0 mL). The mixture was heated to
Synthesis of n-Pentyl 4-(Rh(ttp)CH2)benzenesulfonate (3h).
Rh(ttp)Cl (1a; 15.5 mg, 0.019 mmol), aqueous KOH (5.5 M, 0.035
mL, 0.19 mmol), and n-pentyl tosylate (7; 0.004 mL, 0.018 mmol)
were added to benzene (2.0 mL). The mixture was heated to 150 °C
for 15 min. Excess benzene was removed by rotary evaporation. The
residue was purified by column chromatography on silica gel with a
hexane/CH2Cl2 solvent mixture (1/1) as eluent. The major red band
was collected to give the red solid n-pentyl 4-(Rh(ttp)CH2)-
benzenesulfonate (3h; 4.6 mg, 0.0045 mmol, 24%). Rf = 0.32
1
(hexane/CH2Cl2 1/1). H NMR (CDCl3, 400 MHz): δ −3.85 (d,
2JRh−H = 3.5 Hz, 2H), 0.81 (t, J = 6.9 Hz, 3H), 1.21−1.15 (m, 4H),
1.48 (t, J = 7.0 Hz, 2H), 2.71 (s, 12H), 2.99 (d, J = 7.9 Hz, 2H), 3.65
(t, J = 6.6 Hz, 2H), 6.39 (d, J = 8.1 Hz, 2H), 7.55 (d, J = 7.7 Hz, 4H),
7.58 (d, J = 7.7 Hz, 4H), 7.99 (d, J = 7.6 Hz, 4H), 8.05 (d, J = 7.5 Hz,
4H), 8.71 (s, 8H). 13C NMR (CDCl3, 100 MHz): δ 9.0 (1JRh−C = 28.0
Hz), 13.9, 21.7, 22.2, 27.5, 28.6, 70.6, 122.9, 124.7, 125.5, 127.6, 127.7,
130.0, 131.8, 133.9, 134.0, 137.6, 139.1, 143.2, 148.5. HRMS
(FABMS): calcd for C60H53N4O3RhS [M + H]+ m/z 1013.2966,
found m/z 1013.296177.
Competition Reaction of n-Pentyl Bromide and Cyclopentyl
Bromide with Rh(ttp)Cl. Rh(ttp)Cl (1a; 7.8 mg, 0.0097 mmol),
aqueous KOH (5.5 M, 0.0175 mL, 0.096 mmol), n-pentyl bromide
(2b; 0.012 mL, 0.097 mmol), and cyclopentyl bromide (2f; 0.012 mL,
0.097 mmol) were added to benzene (2.0 mL). The mixture was
heated to 120 °C for 1 h. Excess benzene was removed by rotary
evaporation. The residue was purified by pipet column chromatog-
raphy on silica gel with a hexane/CH2Cl2 solvent mixture (7/1) as
eluent. The red solids Rh(ttp)(n-pentyl)23 (3b; 4.4 mg, 0.0052 mmol,
54%) and Rh(ttp)(cyclopentyl)23 (3i; 1.2 mg, 0.0014 mmol, 14%)
were collected in a single fraction. The ratio was determined by the
integrations of proton signals of their products by 1H NMR
spectroscopy (Table S7 in the Supporting Information).
t
Reaction of Rh(ttp)Cl with BuBr and KOH in Air. Rh(ttp)Cl
(1a; 7.9 mg, 0.0098 mmol), aqueous KOH (5.5 M, 0.0175 mL, 0.096
t
mmol), and Bu-Br (2g; 0.011 mL, 0.098 mmol), were added to
benzene (2.0 mL). The mixture was heated to 120 °C for 1 h. Excess
benzene was removed by rotary evaporation. The residue was purified
by pipet column chromatography on silica gel with a hexane/CH2Cl2
solvent mixture (1/3) as eluent. The red solid HBr·Rh(ttp)Cl (1a·
HBr; 3.7 mg, 0.0042 mmol, 43%) was collected. Rf = 0.26 (hexane/
1
CH2Cl2 1/3). H NMR (CDCl3, 400 MHz): δ −0.28 (br, 8H, ligated
F
Organometallics XXXX, XXX, XXX−XXX