D. Utz, S. Kisslinger, F. W. Heinemann, F. Hampel, S. Schindler,
FULL PAPER
= 799 (53) [Cu2(L2)2Cl3]+, 381 (100) [Cu(L2)Cl]+, 284 (43) [L2]+·.
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IR (KBr): ν = 3278/3256/3183 ν(N–H), 2953/2890 ν(C–H ali-
˜
phatic), 1454 δ(C–H aliphatic), 840 ν(P–F), 751/703 ν(C–H aro-
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(173). μeff (298 K) = 1.82 B.M.
Investigation of the Potential Hydroxylation Reaction of the Ligand:
A
solution of [Cu(L1)(CH3CN)]PF6 (0.793 g, 1.50 mmol) in
CH2Cl2 (20 mL) was bubbled with O2 at –40 °C for 20 min and
warmed to room temperature. After stirring the green suspension
for 1.5 h, it was extracted five times into of a 2:1 mixture of NH3
(25%) and brine (30 mL). The combined aqueous phases were then
washed with CH2Cl2 (50 mL). The combined organic phases were
dried with Na2SO4 and the solvents evaporated to dryness. The
resulting brown oil was dried in vacuo to yield 65% of a mixture
of L1 and the decomposition product benzaldehyde. This was ascer-
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1
tained by H and 13C NMR spectroscopy and mass spectrometry.
In the IR spectrum, no absorption band for a potential O–H vi-
bration was observed.
Quantitative Investigation of H2O2 Formation upon Oxidation: A
solution of L1 (0.559 g, 2.00 mmol) and [Cu(CH3CN)4]PF6
(0.745 g, 2.00 mmol) in CH2Cl2 (50 mL) was bubbled with O2 for
5 min at –40 °C. The resulting green solution was warmed to
–30 °C and the reaction was quenched with HPF6 (4.84 g,
20.00 mmol, 60%) in Et2O (10 mL). After warming to room tem-
perature, the suspension was stirred for 10 min. The brown precipi-
tate was collected by filtration and talen up in Et2O (10 mL). To
this solution was added a solution of KI (1.0 g) in H2O (25 mL)
and concentrated acetic acid (10 mL). After stirring the solution
for 20 min it was titrated with Na2S2O3 solution (0.1 n) using a
freshly prepared starch solution as indicator to yield on average
7.8% H2O2 (referring to 100% formation of the peroxido species).
Selected bond lengths [Å] and angles [°] for 1 to 5 are given in
Tables 1, 2, 3, 4 and 5.
[4]
[5]
CCDC-720275 (for L1), -163359 (for 1), -720276 (for 2),
-720277 (for 3), -720278 (for 4), -720279 (for 5), contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information (see also the footnote on the first page of
this article): Detailed crystallographic data of L1 and complexes 1–
5.
[6]
[7]
Acknowledgments
The authors gratefully acknowledge financial support from the
Deutsche Forschungsgemeinschaft (DFG). Furthermore, they
thank Prof. Rudi van Eldik (University of Erlangen-Nürnberg) for
supporting this work. Diana Utz is thankful for a scholarship from
the University of Erlangen-Nürnberg. Dr. Achim Zahl (University
of Erlangen-Nürnberg) is acknowledged for his assistance with the
NMR measurements.
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