and 8 also have square-pyramidal coordination geometry with
strongly coordinated chloride ligands at apical positions. Also
the structure of the complex 7ؒ6CDCl3 has been solved and in
this case the complex cation crystallizes in two different con-
formations.17 In both, the coordination geometry around the
copper ions is slightly distorted square-planar. A preliminary
X-ray structure of the PF6Ϫ analog of the manganese complex 4
with two apically coordinating imidazole ligands15 indicated
that the complex cation has the structure shown in Scheme 1.
In conclusion, we have synthesized and characterized several
new amphiphilic salen-type transition metal complexes. The
crystal structure of the complex 2ؒ2C2H3Nؒ1.5C6H14O and a
partial crystal structure of 5ؒ6CDCl3 were determined. The
former complex shows a distorted square planar coordination
around the copper ion while for the latter, only a general con-
nectivity could be determined. All the complexes and ligands
existed as solvates in the solid state as indicated by elemental
analyses, NMR spectra and crystal structure analyses.
CH2N), 4.05 (2 H, q, J(HH) = 7.0 Hz, EtOAc), 5.21 (4 H, d,
J(PH) = 12.2 Hz, CH2P), 5.24 (0.4 H, s, CH2Cl2), 6.58 (2 H, m,
Ar), 7.17 (2 H, m, Ar), 7.56–7.69 (30 H, m, Ph), 8.14 (2 H, s,
CH᎐N), 13.97 (2 H, s, OH); δ (CDCl ) 14.26 (EtOAc), 18.52
᎐
C
3
(EtOH), 21.08 (EtOAc), 29.14, 30.35 (d, J(PC) = 46.3 Hz),
34.74, 58.45 (EtOH), 58.87 (CH2Cl2), 59.12, 60.44 (EtOAc),
115.44 (d, J(PC) = 8.0 Hz), 118.25 (d, J(PC) = 85.5 Hz), 118.88
(d, J(PC) = 3.0 Hz), 130.25 (d, J(PC) = 13.1 Hz), 132.38 (d,
J(PC) = 4.0 Hz), 133.42 (d, J(PC) = 6.0 Hz), 134.53 (d,
J(PC) = 9.1 Hz), 134.95 (d, J(PC) = 3.0 Hz), 138.04 (d,
J(PC) = 3.0 Hz), 160.89 (d, J(PC) = 3.0 Hz), 166.97, 171.23
(EtOAc); m/z 965 [C62H64Cl2N2O2P2 Ϫ Cl]ϩ (10), 465
[C62H64Cl2N2O2P2 Ϫ 2Cl]2ϩ (100%).
VIؒ0.5CH2Cl2ؒEtOAcؒ2EtOH. Aldehyde IV (2.00 g, 4.09
mmol) was dissolved in absolute ethanol (20 ml). The mixture
was heated to boiling and (R,R)-1,2-diaminocyclohexane (234
mg, 2.05 mmol) was added. The resulting bright yellow solution
was refluxed for 5 h. The solvent was evaporated and the
residue was dissolved in CH2Cl2 (10 ml). Ethyl acetate (10 ml)
was added and the resulting solution was allowed to evaporate
slowly at room temperature. After 2 days the solid product was
filtered off and washed with ethyl acetate and diethyl ether
to yield VI as yellow crystals (1.91 g, 1.49 mmol, 73%), mp
203–207 ЊC (decomp., from CH2Cl2–EtOAc) (Found: C, 69.32;
H, 6.90; N, 2.21. C66H70Cl2N2O2P2ؒ0.5CH2Cl2ؒEtOAcؒ2EtOH
requires C, 69.97; H, 7.17; N, 2.19%); λmax/nm (MeOH) 329
(ε/dm3 molϪ1 cmϪ1 8100), 300 (infl), 260 (sh), 256 (34700), 252
Experimental
1H and 13C NMR spectra were recorded on a Varian Gemini
2000 operating at 200.0 and 50.0 MHz, respectively. 13C{1H,
31P} triple resonance experiments were conducted using a
Bruker AMX 400 spectrometer at the Finnish Institute for
Verification of the Chemical Weapons Convention (VERIFIN),
operating at 400.1 and 100.6 MHz, respectively. CDCl3 was
used as solvent and the residual solvent signals (δ 7.27 and
77.1 ppm, respectively) as references. The mass spectra were
recorded using a PerSeptive Biosystems Mariner Biospectro-
metry Workstation ES-TOF spectrometer operating in positive-
ion mode in Me2CO–MeOH (9 : 1) solutions (c = 1.0 × 10Ϫ3
mol dmϪ3, spray tip potential 3804 V, nozzle potential 100 V,
skimmer potential 10 V, nozzle temperature 140 ЊC, push pulse
potential 734 V, pull pulse potential 235 V, acceleration poten-
tial 4000 V, reflector potential 1550 V, detector voltage 2100 V).
Elemental analyses were conducted at University of Helsinki,
Department of Pharmacy, using a CE-Instruments Eager EA
1110. FTIR spectra were recorded from neat samples pressed
against a diamond window using a Perkin-Elmer Spectrum One
spectrometer. UV–VIS spectra were recorded using a Varian
Cary 5E UV-Vis-NIR spectrophotometer (c = 2.5 × 10Ϫ5 mol
dmϪ3). Melting points were measured using an Electrothermal
melting point apparatus in open capillaries. Solvents used
were analytical or HPLC grade. Compound IV was prepared
according to the published procedure with slight modification.9
Ethylenediamine was distilled from sodium before use. Other
starting materials were of commercial quality (purity >98%)
and used as purchased.
(infl); ν/cmϪ1 3301, (H2O), 1717 (EtOAc), 1628 (C᎐N);
᎐
δH(CDCl3) 1.07 (18 H, s, But), 1.17 (6 H, t, J(HH) = 7.0 Hz,
EtOH), 1.22 (3 H, t, J(HH) = 7.0 Hz, EtOAc), 1.37 (2 H, m,
cyclohexyl), 1.58 (2 H, m, cyclohexyl), 1.78 (2 H, m, cyclo-
hexyl), 1.86 (2 H, m, cyclohexyl), 2.00 (1.5 H, s, EtOAc), 3.21
(2 H, m, CHN), 3.65 (4 H, q, J(HH) = 7.0 Hz, EtOH), 4.08
(2 H, q, J(HH) = 7.0 Hz, EtOAc), 4.79 (2 H, dd, J(HH) = Ϫ14.3
Hz, J(PH) = 14.3 Hz), 5.21 (1H, s, CH2Cl2), 5.46 (2 H, dd,
J(HH) = Ϫ14.3 Hz, J(PH) = 14.3 Hz), 6.67 (2 H, m, Ar), 6.80
(2H, m, Ar), 7.50–7.73 (30 H, m, Ph), 7.97 (2 H, s, CH᎐N),
᎐
13.99 (2 H, s, OH); δC(CDCl3) 14.11 (EtOAc), 18.42 (EtOH),
20.94 (EtOAc), 23.93, 29.05, 30.26 (d, J(PC) = 46.4 Hz), 32.65,
34.61, 56.22 (CH2Cl2), 58.07 (EtOH), 60.28 (EtOAc), 71.37,
115.22 (d, J(PC) = 8.6 Hz), 117.84 (d, J(PC) = 85.2 Hz), 118.60
(d, J(PC) = 2.9 Hz), 130.13 (d, J(PC) = 12.4 Hz), 132.30 (d,
J(PC) = 4.6 Hz), 132.58 (d, J(PC) = 5.9 Hz), 134.24 (d, J(PC) =
9.7 Hz), 134.93 (d, J(PC) = 3.0 Hz), 137.89 (d, J(PC) = 3.1 Hz),
160.70 (d, J(PC) = 3.2 Hz), 164.89, 171.02 (EtOAc); m/z 1019
[C66H70Cl2N2O2P2 Ϫ Cl]ϩ (8), 492 [C66H70Cl2N2O2P2 Ϫ 2Cl]2ϩ
(100%).
1ؒCH2Cl2ؒ2H2O. Ligand V (238 mg, 0.200 mmol) was dis-
solved in absolute ethanol (4 ml). The resulting solution was
heated to boiling and Co(OAc)2ؒ4H2O (50 mg, 0.201 mmol) was
added. The yellow solution turned to dark brown immediately
and was refluxed for 2 h. The solvent was evaporated and the
residue dissolved in CH2Cl2 (2 ml) and ethyl acetate (1 ml)
added. The filtered solution was allowed to evaporate slowly at
room temperature. The precipitated solid was filtered off and
washed with ethyl acetate and diethyl ether. Recrystallization
from CH2Cl2–ethyl acetate yielded 1 as a brown powder (189
mg, 0.160 mmol, 80%), mp 151–155 ЊC (decomp., from
CH2Cl2–EtOAc) (Found: C, 64.04; H, 5.83; N, 2.50. C62H62Cl2-
CoN2O2P2ؒCH2Cl2ؒ2H2O requires C, 64.13; H, 5.81; N, 2.37%);
λmax/nm (MeOH) 401 (sh), 326 (ε/dm3 molϪ1 cmϪ1 32800), 301
(infl), 266 (68100), 246 (infl), 226 (75400), 218 (infl); ν/cmϪ1
Preparation of ligands and complexes
Vؒ0.2CH2Cl2ؒEtOAcؒEtOHؒ2H2O. Aldehyde IV9 (2.00 g,
4.09 mmol) was dissolved in absolute ethanol (20 ml). The
mixture was heated to boiling and ethylenediamine (138 µl, 2.05
mmol) added. The resulting bright yellow solution was refluxed
for 2 h, the solvent evaporated and the residue dissolved in
CH2Cl2 (8 ml). Ethyl acetate (6 ml) was added and the resulting
solution was allowed to evaporate slowly at room temperature.
After 3 days the solid product was filtered off and washed with
ethyl acetate and diethyl ether yielding V as a yellow powder
(2.04 g, 1.72 mmol, 84%), mp 202–204 ЊC (decomp., from
CH2Cl2–EtOAc) (Found: C, 68.67; H, 6.49; N, 2.65. C62H64Cl2-
N2O2P2ؒ0.2CH2Cl2ؒEtOAcؒEtOHؒ2H2O requires C, 68.88; H,
6.98; N, 2.36%); λmax/nm (MeOH) 326 (ε/dm3 molϪ1 cmϪ1 9500),
299 (infl), 267 (infl), 261 (40400), 251 (infl); ν/cmϪ1 3365 (H2O ϩ
3428 (H O), 1641 (C᎐N); m/z 1022 [C H Cl CoN O P Ϫ Cl]ϩ
᎐
2
62 62
2
2
2
2
(2), 493 [C62H62Cl2CoN2O2P2 Ϫ 2Cl]2ϩ (61).
EtOH), 1726 (EtOAc), 1629 (C᎐N); δ (CDCl ) 1.06 (18 H, s,
᎐
H
3
But), 1.13 (3 H, t, J(HH) = 7.0 Hz, EtOH), 1.19 (3 H, t,
J(HH) = 7.0 Hz, EtOAc), 1.97 (3 H, s, EtOAc), 2.31 (4 H, br s,
H2O), 3.61 (2 H, q, J(HH) = 7.0 Hz, EtOH), 3.72 (4 H, s,
2ؒ4H2O. Prepared as for complex 1 using Cu(OAc)2ؒH2O
instead of Co(OAc)2ؒ4H2O. Gray–purple solid, yield 83%, mp
161–164 ЊC (decomp., from CH2Cl2–EtOAc) (Found: C, 65.70;
J. Chem. Soc., Dalton Trans., 2001, 991–995
993