Organometallics
ARTICLE
The reaction mixture was stirred at room temperature for 20 h. The
solvent was removed under vacuum. Purification by flash column
chromatography column yielded biaryl product. The NMR data of the
product matched those of the literature report.34
’ ACKNOWLEDGMENT
We gratefully acknowledge the NSF, the NIGMS (No.
5RO1GM076125), and the Department of Energy for support
of this research. We thank Professor Joel S. Miller for help with
EPR analysis. X-ray crystal analysis was performed by Dr. Atta
M. Arif.
General Procedure of Suzuki Coupling. p-Bromoanisole (18.7
mg, 0.100 mmol) and phenylboronic acid (13.4 mg, 0.110 mmol) were
weighed into a scintillation vial equipped with a magnetic stir bar. A solution of
the Ni catalyst (0.01 mmol, 0.007 M) in benzene (0.67 mL) was added. The
reaction mixture was stirred at 80 °C for 8 h. The solvent was removed under
vacuum. Purification by flash column chromatography yielded biaryl product.
The NMR data of the product matched those of the literature report.35
General Procedure for Stoichiometric Reaction of Ni(I)
Complex with Aryl Halide. In a glovebox, stock solution 1 was
prepared by dissolution of NiI(IMes)2Br (40.0 mg, 0.0535 mmol, 0.0535
M) and ferrocene (10.0 mg, 0.0535 mmol, 0.0535 M) in C6D6 (1 mL) in
a 5 mL glass vial. Stock solution 2 was prepared by dissolution of aryl
halide (0.054 mmol, 0.054 M) in C6D6 (1 mL) in a 5 mL glass vial. A
0.25 mL portion of stock solution 1 and 0.25 mL of stock solution 2 were
added into an NMR tube. The NMR tube was equipped with a screw-
thread cap with a PTFE/silicone septum and taken out of the glovebox.
The NMR spectra were obtained every 1 h.
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General Procedure for Stoichiometric Reaction of Ni
Complexes with Aryl Grignard Reagent. In a glovebox, stock
solution 1 was prepared by dissolution of NiI(IMes)2Br (40.0 mg,
0.0535 mmol, 0.0535 M) and ferrocene (10.0 mg, 0.0535 mmol, 0.0535
M) in C6D6 (1 mL) in a 5 mL glass vial. Stock solution 2 was prepared by
adding
a mesitylmagnesium bromide solution (0.0535 mmol,
0.0535 mL, 1.0 M in diethyl ether) in C6D6 (1 mL) into a 5 mL glass
vial. A 0.25 mL portion of stock solution 1 and 0.25 mL of stock solution
2 were added into an NMR tube. The NMR tube was equipped with a
screw-thread cap with a PTFE/silicone septum and taken out of the
glovebox. The NMR spectrum was obtained immediately.
Stoichiometric Reaction of Ni(I) Complex with Phenyl-
boronic Acid without KO-t-Bu. In a glovebox, stock solution 1 was
prepared by dissolution of NiI(IMes)2Br (40.0 mg, 0.0535 mmol, 0.0535
M) and ferrocene (10.0 mg, 0.0535 mmol, 0.0535 M) in C6D6 (1 mL) in a
5 mL glass vial. Stock solution 2 was prepared by dissolution of phenyl-
boronic acid (6.5 mg, 0.054 mmol, 0.054 M) in C6D6 (1mL) ina5mLglass
vial. A 0.25 mL portion of stock solution 1 and 0.25 mL of stock solution 2
were added into an NMR tube. The NMR tube was equipped with a screw-
thread cap with a PTFE/silicone septum and taken out of the glovebox. The
NMR spectrum was obtained immediately.
Stoichiometric Reaction of Ni Complex with Phenylboro-
nic Acid with KO-t-Bu. In a glovebox, stock solution 1 was prepared
by dissolution of NiI(IMes)2Br (40.0 mg, 0.0535 mmol, 0.0535 M) and
ferrocene (10.0 mg, 0.0535 mmol, 0.0535 M) in C6D6 (1 mL) in a 5 mL
glass vial. Stock solution 2 was prepared by dissolution of phenylboronic
acid (6.5 mg, 0.054 mmol, 0.054 M) and KO-t-Bu (29.9 mg, 0.267 mmol,
0.267 M) in C6D6 (1 mL) in a 5 mL glass vial. A 0.25 mL portion of stock
solution 1 and 0.25 mL of stock solution 2 were added into an NMR
tube. The NMR tube was equipped with a screw-thread cap with a
PTFE/silicone septum and taken out of the glovebox. The NMR
spectrum was obtained immediately.
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’ ASSOCIATED CONTENT
S
Supporting Information. Figures giving EPR spectra for
b
compounds 2ꢀ4 and CIF files, tables, and figures giving crystal-
lographic data and structural details for 2ꢀ4, 7, and 9. This material
(14) Other examples of Ni(I) formation in cross-coupling chemis-
try: (a) Morrell, D. G.; Kochi, J. K. J. Am. Chem. Soc. 1975,
97, 7262–7270. (b) Colon, I.; Kelsey, D. R. J. Org. Chem. 1986,
51, 2627–2637. (c) Jones, G. D.; McFarland, C.; Anderson, T. J.;
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: louie@chem.utah.edu.
2551
dx.doi.org/10.1021/om200090d |Organometallics 2011, 30, 2546–2552