Organometallics
Article
amount of toluene was detected. Complex 1 was isolated in 73% yield
(5.93 mg, 0.00579 mmol).
cell; one Et2O molecule was disordered with an occupancy ratio of
87:13. Anisotropic refinement was applied to all non-hydrogen atoms
except for disordered groups. Hydrogen atoms were placed at
calculated positions. The crystallographic data and the summary of
solution and refinement are listed in Table 1.
Reaction of 1 with MesMgBr. Complex 1 (15.6 mg, 0.0152 mmol)
was dissolved in C6H6 (2 mL), and a THF solution of MesMgBr
(0.2 M, 200 μL, 0.040 mmol) was slowly added over 1 h at room
temperature. The solvent was removed under vacuum, and the residue
was washed with hexane (0.5 mL × 3), extracted with C6H6, and
filtered through a Celite pad. The filtrate was concentrated to dryness
under vacuum to afford 3 as a dark brown solid (13.1 mg, 0.0130
mmol, 88%). The hexane washings were concentrated under vacuum,
ASSOCIATED CONTENT
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S
* Supporting Information
Cyclic voltammogram of [FeCl2(iPrPDI)], ESI-mass spectrum
of 3, and crystallographic data (CIF files). This material is
1
dissolved in C6D6 (0.4 mL), and analyzed by H NMR spectroscopy
using CH2Cl2 (2 μL, 0.031 mmol) as an internal standard, showing the
formation of bimesityl (0.0061 mmol, 80%). Single crystals of 3 for
X-ray diffraction analysis were grown by slow evaporation of a toluene
solution at room temperature. 1H NMR (C6D6, 20 °C): δ −4.89 (brs),
−2.38 (brs), −1.29 (brs), 0.52 (s), 4.75 (s), 5.86 (brs), 8.37 (brs),
21.13 (brs). ESI-MS (m/z): 982.5 (M+). This complex did not give a
satisfactory elemental analysis.
AUTHOR INFORMATION
Corresponding Author
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Notes
Reaction of 2 with MesMgBr. To a C6H6 solution (2 mL) of
2 (12.2 mg, 0.0129 mmol) was added a THF solution of MesMgBr
(0.06 M, 200 μL, 0.012 mmol) over 1 h at room temperature. The
solution was stirred for 1 h and filtered through a Celite pad. The solvent
was evaporated, and the residue was washed with hexane (0.5 mL) and
dried under vacuum to give 3 (7.06 mg, 0.0718 mmol, 55%).
Reaction of 1 with Mes2Mg(THF)2. To a C6H6 solution (1 mL)
of 1 (30.6 mg, 0.0299 mmol) was added a C6H6 solution (0.5 mL) of
Mes2Mg(THF)2 (12.0 mg, 0.0295 mmol). The mixture was stirred at
room temperature for 1 h and filtered through a Celite pad. Removal
of the solvent under vacuum afforded 3 as a dark brown solid (20.3 mg,
0.0206 mmol, 69%).
Reaction of 2 with Mes2Mg(THF)2. Complex 2 (26.8 mg, 0.0284
mmol) was dissolved in C6H6 (1 mL), and a C6H6 solution of
Mes2Mg(THF) (6.92 mg, 0.0170 mmol) was added. The mixture was
stirred at room temperature for 30 min and filtered through a Celite
pad. The solvent was evaporated, and the residue was washed with
hexane (0.5 mL) and dried under vacuum to give 3 (19.4 mg, 0.0198
mmol, 70%).
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by a Grant-in-Aid for Scientific
Research from MEXT Japan and the JST PRESTO program.
We are grateful to Dr. Sasamori and Dr. Mizuhata (ICR, Kyoto
Univ.) for crystallographic assistance and to Prof. Ono (ICR,
Kyoto Univ.) for SQUID measurement.
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dx.doi.org/10.1021/om201280z | Organometallics 2012, 31, 2009−2015