J. K. Bera et al.
FULL PAPER
[{Cu(L1)}2][OTf]2 (1): A dichloromethane solution (10 mL) of L1
(44 mg, 0.11 mmol) was added dropwise to a dichloromethane
solution (15 mL) of [Cu(CH3CN)4][OTf] (43 mg, 0.11 mmol) and
the reaction mixture was stirred for 4 h at room temperature. The
resulting solution was concentrated and diethyl ether (15 mL) was
added with stirring to induce precipitation. The dark-red solid resi-
due was washed with diethyl ether (3ϫ10 mL) and dried in a vac-
uum to afford 1; yield 65 mg (96%). X-ray quality crystals were
grown by layering diethyl ether onto a saturated dichloromethane
solution of 1 inside an 8 mm o.d. vacuum-sealed glass tube. IR
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(KBr): ν = 3430 (m, NH), 1647 (s, CONH), 1612 (s, NP), 1572
˜
(m), 1504 (m), 1416 (br), 1250 (vs, OTf–) cm–1. 1H NMR (CD2Cl2,
297 K): δ = 10.37 (br., 1 H, NH), 8.65 (d, J = 8.0 Hz, 1 H, NP-H),
8.40 (d, J = 10.0 Hz, 1 H, NP-H), 7.44 (s, 1 H, NP-H), 5.30 (s, 2
H, Cp), 4.61 (s, 2 H, Cp), 4.27 (s, 5 H, Cp) 2.89 (s, 3 H, NP-Me),
2.79 (s, 3 H, NP-Me) ppm. 13C NMR (125 MHz, CD2Cl2, 292 K):
δ = 172.5 (NHCO), 165.4 (NCNNP), 154.2 (NCCNP), 153.2
(NCCNP), 152.1 (CCCNP), 136.5 (CHNP), 125.2 (CHNP), 123.8
(CCCNP), 119.5 (CHNP), 71.7 (CCCCp), 70.2 (CHCp), 69.6 (CHCp),
68.3 (CHCp), 25.2 (CH3), 17.3 (CH3) ppm. MS (ESI): m/z = 1048
[M2+ + OTf–]+, 895 [M]+. C44H38Cu2F6Fe2N6O8S2 (1195.71): calcd.
C 44.20, H 3.20, N 7.03, S 5.36; found C 43.64, H 3.14, N 6.86, S
5.19.
[{Cu(L2)Cl}2] (2): A sample of L2H (45 mg, 0.16 mmol) was added
to a dichloromethane solution (30 mL) of [Cu(CH3CN)4][BF4]
(45 mg, 0.14 mmol) and the mixture was stirred overnight at room
temperature. The resulting solution was concentrated and diethyl
ether (15 mL) was added with stirring to induce precipitation. The
green solid residue was washed with diethyl ether (3ϫ10 mL) and
dried in a vacuum to afford 2; yield 39 mg (74%). X-ray-quality
crystals were grown by layering petroleum ether onto a saturated
dichloromethane solution of 2 inside an 8 mm o.d. vacuum-sealed
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glass tube. IR (KBr): ν = 1630 (s, CONH), 1590 (s, NP), 1510 (m),
˜
1411 (m), 1360 (s), 1316 (s) cm–1. MS (ESI): m/z = 729 [M – Cl]+.
C32H38Cl2Cu2N8O2 (764.70): calcd. C 50.26, H 5.01, N 14.65;
found C 49.80, H 4.94, N 14.26.
General Procedure for the Cyclopropanation Reaction: A dichloro-
methane solution (3 mL) of EDA (1 mmol, 0.11 mL) was added
dropwise to
a mixture of alkene (10 mmol) and catalyst
(0.01 mmol) in dichloromethane under nitrogen over a period of
30 min. Then the solution was stirred for 6 h at 25 °C. The progress
of the reaction was monitored by TLC. After the reaction was over,
the reaction mixture was extracted with diethyl ether (3ϫ10 mL).
The ethereal solution was washed with brine, dried with MgSO4,
and filtered. After removing the solvent under vacuum, the product
was purified by chromatography on a silica gel column using hex-
ane/EtOAc as eluent.
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Supporting Information (see footnote on the first page of this arti-
cle): NMR spectra, ESI-MS and all bond lengths and bond angles
for L2H and compounds 1 and 2.
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Chem. 2010, 695, 67.
Acknowledgments
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Angew. Chem. Int. Ed. 2007, 46, 930; M. L. Clarke, J. A. Fuen-
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This work was financially supported by the Department of Science
and Technology (DST), New Delhi and the Indo-French Centre
for the Promotion of Advanced Research (IFCPAR). J. K. B.
thanks the DST for a Swarnajayanti Fellowship. R. K. D. and
M. S. thank the Council of Scientific and Industrial Research
(CSIR), New Delhi and W. R. thanks the University Grants Com-
mission (UGC), India for fellowships.
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1686
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