Organometallics
Article
mg (0.054 mmol) of TAPH and 45.0 mg (0.55 mmol) of anhydrous
sodium acetate in 15 mL of chloroform under nitrogen. The resulting
mixture was stirred at room temperature for 1 h. A 28.0 mg portion
2
ASSOCIATED CONTENT
Supporting Information
■
*
S
(
0.11 mmol) of I was dissolved in 2.0 mL of chloroform and added to
2
the mixture in two stages: 1.0 mL initially and an additional 1.0 mL
after 30 min. The reaction mixture was then stirred at room
temperature for an additional 3 h. The crude product was
concentrated by rotary evaporation after filtration to remove the
inorganic salts and chromatographed on neutral alumina using 4/1 (v/
Typical procedures for the catalytic hydrolysis of silanes
mediated by (TAP)Rh−I (PDF)
v) dichloromethane/ethyl acetate as the eluent to give (TAP)Rh−I in
1
an overall yield of 65%. H NMR (400 MHz, CDCl ) δ (ppm): 4.08
3
AUTHOR INFORMATION
Author Contributions
These authors contributed equally to this work.
(
s, 12H; CH ), 7.23−7.29 (m, 8H; meta-H), 8.07−8.15 (m, 8H; ortho-
3
■
*
1
H), 8.89 (s, 8H; β-pyrrole H). H NMR (400 MHz, THF-d ) δ
8
(
(
ppm): 4.06 (s, 12H; CH ), 7.27−7.33 (m, 8H; meta-H), 8.07−8.09
3
m, 8H; ortho-H), 8.83 (s, 8H; β-pyrrole H).
−3
Hydrolysis Reaction of Silanes. A 3.1 mg portion (3.2 × 10
mmol) of (TAP)Rh−I dissolved in 2.0 mL of THF was mixed with
44 μL (8.0 mmol) of water in a 10 mL two-neck flask with one neck
†
1
Notes
attached to a gas buret filled with dibutyl phthalate. A 500 W mercury
lamp was used for irradiation. Silanes (0.8 mmol) were added to the
solution through a syringe, resulting in the immediate formation of
dihydrogen. Concentrations of the residual silane and silanol
production were measured by the ratio of the intensity integration
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the Nature Science Foundation of
China (Grants 21322108 and 21321001).
1
of the H NMR with respect to a known concentration of
hexamethylbenzene as an internal standard. In the cases of Et Si−H
3
and Et Si−OH, concentrations were measured by gas chromatography
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3
■
with a standard curve.
(
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2
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−3
Acid. A 1.0 mL portion of a THF solution of (TAP)Rh−I (1.6 × 10
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2
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4
1
1
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−
4
Synthesis of (TAP)Rh−H. A 92 μL portion of 6.5 mM (6.0 × 10
5
(
mmol) (TAP)Rh−I chloroform solution was evaporated and then
−3
dissolved in 0.3 mL of THF-d and mixed with 1.0 μL (7.6 × 10
8
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mmol) of EtMe Si−H in a J. Young valve NMR tube to instantly
2
1
produce an orange solution of stoichiometric (TAP)Rh−H. H NMR
1
(
400 MHz, THF-d ) δ (ppm): −38.09 (d, 1H, J(Rh,H) = 31.7 Hz;
8
Rh-H), 4.04 (s, 12H; CH ), 7.25−7.30 (m, 8H; meta-H), 7.99−8.05
3
(
m, 8H; ortho-H), 8.67 (s, 8H; β-pyrrole H).
6
2
130−6132. (f) Tan, S. T.; Kee, J. W.; Fan, W. Y. Organometallics
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8
3
1
monitored by H NMR at 35 °C in the dark under nitrogen. Different
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3
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́
−4
Generation of [(TAP)Rh] . A 6.0 × 10 mmol portion of
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Mizuno, N. Adv. Synth. Catal. 2009, 351, 1405−1411.
2
(
TAP)Rh−H was dissolved in 0.3 mL of anhydrous C D and
6
6
1
irradiated for 1 h to generate [(TAP)Rh] . H NMR (400 MHz,
2
C D ) δ (ppm): 3.61 (s, 24H; CH ), 7.15 (meta-phenyl H obscured by
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Yamamoto, Y.; Chen, M.; Zhang, W.; Inoue, A. Angew. Chem., Int. Ed.
6
6
3
3
solvent), 7.60 (d, 8H, J (H,H)= 7.4 Hz; ortho-H), 8.69 (s, 16H; β-
pyrrole H), 9.70 (d, 8H, J(H,H) = 7.8 Hz; ortho-H).
3
̀
2010, 49, 10093−10095. (b) John, J.; Gravel, E.; Hagege, A.; Li, H.;
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Wang, A.; Yang, X.; Huang, Y.; Zhang, T. Chem. Commun. 2012, 48,
9183−9185.
2
−3
SiEtMe . A 153 μL portion of 6.5 mM (1.0 × 10 mmol) (TAP)Rh−
I chloroform solution was evaporated, and then the residue was
2
−3
dissolved in 0.4 mL of C D and mixed with 1.3 μL (9.8 × 10 mmol)
6
6
of EtMe Si−H in a J. Young valve NMR tube. The reaction mixture
2
was heated at 60 °C for 10 h to form (TAP)Rh−SiEtMe in a yield of
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2
1
7
6%. H NMR (400 MHz, CDCl ) δ (ppm): −3.84 (s, 6H; methyl
3
3
3
CH ), −3.71 (q, 2H, J(H,H) = 7.9 Hz; CH ), −1.27 (t, 3H, J(H,H)
3
2
=
8.0 Hz; ethyl CH ), 4.09 (s, 12H; OCH ), 7.23−7.28 (m, 8H; meta-
3
3
H), 7.98−8.10 (m, 8H; ortho-H), 8.67 (s, 8H; β-pyrrole H). HRMS
+
(
ESI): calcd for C H N O RhSi [M + H] 923.25136; found
52 48 4 4
9
23.24944.
D
Organometallics XXXX, XXX, XXX−XXX