Table 2 Catalytic results obtained with compounds 1–3 in aziridina-
a
tion reactions
converged with R1 ¼ 0.0498 (I
> 2s(I
)), wR2 ¼ 0.1115 (all
o
o
data), GOF ¼ 1.046, and a shift/error of o0.001. The final
difference Fourier map shows no striking features (Demin/max
¼
b
Entry Substrate
1
Catalyst Time (h) Yield(%)
ꢁ3
˚
þ0.56/ꢁ0.92 e A ). Besides two crystallographic independent
molecules A and B of 3 we found in the solid state additionally
one molecule of solvent CH Cl and one molecule of water.
1
5
75
2
2
The overall geometry of the two molecules A and B is identical
within the esd’s (see supporting materialw). CCDC reference
number 277167. For crystallographic data in CIF or other
electronic format see DOI: 10.1039/b509568a
2
3
4
2
3
1
6
74
94
54
3.5
10
5
6
2
3
10
1
47
84
Procedure for the synthesis of the complexes 1, 2
A solution of H
2
2
L (1 mmol) and Cu(OAc)
0 ml of ethanol was heated to reflux for 3 h. The precipitated
2
ꢀ H
2
O (1 mmol) in
7
3
6.5
82
solids were isolated by vacuum filtration and rinsed with
ethanol several times. The solid was collected and dried in
vacuum to get the complexes 1 and 2. The spectroscopic data
of compound 1 of this work are identical to those described in
8
3
3
76
1
8
the literature for the compound named 1e in the latter paper.
Complex 1, Anal. Calc. for C20 20CuN : C, 62.57; H,
5.25; N, 7.30. Found: C, 62.25; H, 4.84; N, 7.26%. IR (KBr,
H
2 2
O
9
3
3
24
88
22
ꢁ1
cm ): 2929 (w), 1631 (s), 1604 (m), 1541 (m).
Complex 2, Anal. Calc. for C H CuN O C, 61.92; H,
2
0
24
2
2
6.24; N, 7.22. Found: C, 61.69; H, 6.19; N, 7.15%. IR (KBr,
ꢁ1
cm ): 3206 (s), 1589 (s), 1477 (s).
10
20
a
Olefin (2.5 mmol), (188.0 mg, 0.5 mmol) PhIQNTs and (0.01 mmol)
catalyst (1–3) were stirred in 2.0 ml acetonitrile at the room tempera-
b
ture. Isolated yield.
General procedure for the synthesis of the complex 3
A solution of H
2
2
L (1 mmol) and Cu(OAc)
2
ꢀ H
2
O (1 mmol) in
0 ml of ethanol was heated to reflux for 3 h. The resulting
dark green solution was subsequently evaporated under oil
pump vacuum. The remaining residue was extracted with
All organic and inorganic starting materials were purchased
from Aldrich or Acros and used without further purification.
The salen ligand for compound 3 was prepared as described in
2
1–23
2 2
CH Cl , filtered via cannula, and the resulting liquid was
brought to dryness under oil pump vacuum to get a dark green
solid. Single crystals suitable for X-ray analysis were obtained
the literature.
by recrystallization from a CH
2 2
Cl –hexane mixture. Anal.
X-ray crystallography
Calc. for C H CuN O ꢀ H O: C, 58.34; H, 6.94; N, 5.67.
2
4
32
2
4
2
ꢁ
1
Crystal data: C H Cl Cu N O , M ¼ 1055.07, monoclinic,
4
9
68
2
2
4
9
r
Found: C, 58.07; H, 6.78; N, 5.74%. IR (KBr, cm ): 3423 (s),
936 (s), 1594 (s), 1480 (vs), 1452 (vs), 1293 (s), 864 (s); CI-MS
˚
a ¼ 21.3987(1), b ¼ 11.1987(1), c ¼ 21.5985(2) A, b ¼
2
3
˚
1
1
1
P2
06.0160(3)1, U ¼ 4974.91(7) A , T ¼ 173 K, space group
(
(
C
70 eV): m/z (%): 414 (8) [M ꢁ O
1
2 3
CCH ] ; 354 (2) [LH] ; 309
ꢁ
3
1
1
/c (no. 14), Z ¼ 4, D
c
¼ 1.409 g cm , m(Mo–K ) ¼ 1.021
a
4) [M ꢁ O CCH ꢁ C H (CH )OH] ; 248 (41) [LH
ꢁ
2
3
6
4
3
2
ꢁ1
1
mm . Data collection: Suitable single crystals for the X-ray
diffraction study were grown by standard techniques from a
saturated mixture of hexane–dichloromethane at room tem-
perature. A clear dark green fragment was stored under per-
fluorinated ether, transferred in a Lindemann capillary, fixed,
and sealed. Preliminary examination and data collection were
carried out on a KappaCCD device (NONIUS MACH3) with
an Oxford Cryosystems cooling device at the window of a
rotating anode (NONIUS FR591) with graphite monochro-
H
6 4
(CH
2
)O] ; 107 (100) [C
6
H
4
2
(CH )OH] .
General procedure for the olefin aziridination reaction
Olefin (2.5 mmol; e.g. 260.0 mg styrene), (188.0 mg, 0.5 mmol)
PhIQNTs and (0.01 mmol) catalyst (1–3, resp.,) were stirred at
room temperature in 2.0 ml acetonitrile for the time spans
given in Table 1. Then the product was purified by silica gel
column chromatography (hexane : ethyl acetate ¼ 5 : 1) and
yields were determined by weighting the isolated product. The
2
4
˚
mated Mo–K
a
radiation (l ¼ 0.710 73 A). Data collection
was performed at 173 K (OXFORD CRYOSYSTEMS) within
a y-range of 1.941 o y o 25.361. The detector to crystal
distance was set to 40 mm. Nine data sets in rotation scan
modus with Dj/Do ¼ 1.01 were measured and a total number
of 112470 intensities were integrated. Raw data were corrected
for Lorentz, polarization, and, arising from the scaling proce-
1
structure of pure product was determined by H-NMR and
GC-MS.
Conclusions
Dependent on the product workup, copper(II) salen com-
pounds can be isolated with or without an additional acetate
ligand. All examined complexes are applicable as catalysts in
the aziridination of styrene, where the acetate ligated complex
3 is found to display the highest product yield. Complex 3 is
also an active catalyst for the aziridination of several activated
olefins.
2
5
dure, for latent decay and absorption effects. After merging
int ¼ 0.076) a sum of 9110 (all data) and 7377 [I 4 2s(I)],
respectively, remained and all data were used. Solution: The
(
R
2
6
structure was solved by a combination of direct methods and
2
7
difference-Fourier syntheses. All non-hydrogen atoms were
refined with anisotropic displacement parameters. All hydro-
gen atoms bound to oxygen atoms were found and were
allowed to refine freely with individual isotropic displacement
parameters. All other hydrogen atoms were calculated in ideal
positions (riding model). Refinement: Full-matrix least-squares
refinements with 617 parameters were carried out by minimiz-
Acknowledgements
FEK thanks the FCI for financial support. WS is grateful to
the Alexander von Humboldt foundation for a postdoctoral
research fellowship.
2
2 2
ing Sw(Fo ꢁ F ) with the SHELXL-97 weighting scheme and
c
N e w J . C h e m . , 2 0 0 5 , 2 9 , 1 5 7 7 – 1 5 8 0
1579