Rodopoulos et al.
897
3
work-up (1.944 g, 85%) was observed to be a mixture. Puri-
fication was achieved by preparation of the corresponding
copper(II) complex (0.642 g) followed by decomplexation
Me 4
N
5
8
7
2
9
3
N
6
1
O
of the metal ion by use of Na S (9). The final yield of L
2
3
1
3
was 0.426 g (21% from macrocycle 2). C NMR (CDCl3):
2.1 (CH -O), 56.6, 56.2, 56.0, 55.5, 54.7 (CH -N), 43.2 (N-
N
N
7
2
2
Me
+
CH ), 26.6, 25.8 (CH -CH -CH ). MS: 298 (M ), 299 (M +
1
3
2
2
2
+
+
) , 327 (M + 29) .
L
3
4
,8-Dimethyl-1,4,8,11-tetraaza-17-oxabicyclo[9.5.3]nona-
decane-cobalt(III) perchlorate ([Co(L )(ClO )](ClO ) )
3
4
4 2
under constant stirring to a mixture of CHCl (69 mL) and
3
The ligand L (0.132 g, 0.442 mmol) was dissolved in an
ethanol–water mixture (48 mL : 12 mL) and heated to re-
H O (34 mL) and cooled in an ice bath. A mixture of
3
2
chloroacetyl chloride (22.11 g, 0.1957 mol) in CHCl3
flux. An aqueous solution of Co(ClO ) ·6H O (0.162 g,
(
86 mL) and K CO (22.36 g, 0.162 mol) in water (860 mL)
4 2
2
2
3
0
.442 mmol) was added and the solution turned a yellow-
was added simultaneously under a nitrogen atmosphere over
a 1 h period. The reaction mixture was stirred at room tem-
green colour. Several grams of activated charcoal were intro-
duced and the solution was refluxed for 2 h. Air bubbling of
the cooled solution (5 h) followed by filtration yielded a
pink-red solution. After removal of the residual ethanol and
perature for a further 2 h. The CHCl layer was separated,
3
washed with water (2 × 100 mL), and dried over MgSO4.
Removal of the solvent yielded a colourless oil that was
addition of 1 drop of concd. HClO , the solution was left to
dried in vacuo overnight. Upon addition of CCl and cooling
4
4
crystallize at 4 °C overnight. The crystals were washed with
overnight, a white solid precipitated. Filtration and concen-
tration of the filtrate followed by a further addition of CCl4
afforded a second crop of material. The diamide 4 was
washed with ethanol and dried. Yield: 9.5 g, 76%. The NMR
ethanol, ether, and air dried. Yield: 0.106 g, 37%. 13C NMR
(
3
D O): 66.9 (CH -O), 60.9, 55.0, 54.6, 52.3, 51.7 (CH -N),
2 2 2
9.0 (N-CH ), 19.7 (CH -CH -CH ). It appears that there is
3 2 2 2
1
3
overlap of the methylene peaks, since only eight and not
spectrum showed the presence of several isomers. C NMR
nine signals were observed. MS (negative ion): 654.05
(
4
CDCl ): 166.2, 166.7 (-C=O), 45.7, 45.6 (CH -NMe), 41.0,
3
2
–
(
5
[Co(L )(ClO )](ClO ) ] . UV–vis (λ , nm): 232 (ε =
1.4, 41.6 (-CH -C(O)-), 24.3, 26.6 (-C-CH -C-).
3
4
4 2
max
2
2
–1
–1
–1
–1
380 (mol/L) cm ) and 516 (ε = 17 (mol/L) cm ).
The isomeric macrobicyclic ligand, 5,8-dimethyl-1,5,8,12-
To a solution of the bis(chloro)diamide 4 (1.718 g,
6
.73 mmol), in dry distilled CH CN (200 mL), was added
3
tetraaza-17-oxabicyclo[10.5.2]nonadecane (L ), was pre-
sodium iodide (5.548 g, 37.01 mmol). The macrocycle 2
4
4
pared in a manner similar to that outlined previously using
(
(
0.971 g, 6.73 mmol) was dissolved in dry distilled CH CN
200 mL) and solutions of the reagents 4 and 2 were added
3
N,N′-dimethylethylenediamine and 3-chloropropionyl chlo-
ride as initial reactants. Further reaction of the resultant
bis(chloro)diamide with the macrocycle 1,4-diaza-7-
oxacyclononane yielded the bicyclic diamide that upon re-
very slowly (over a 24 h period) under N in 50 mL batches
2
to a refluxing solution of dry distilled acetonitrile (2.5 L)
containing Na CO (9.415 g, 88.83 mmol). Heating of the
2
3
duction, as described previously, yielded ligand L . For the
mixture, now orange coloured, was continued for a further
0 h, and the mixture was cooled overnight. Filtration under
nitrogen, removal of the solvent, and addition of CHCl3
250 mL) yielded an orange solution and an off-white solid.
4
Co(III) complex [Co(L )(Cl)](ClO ) calcd. (%): C 32.48, H
1
4
4 2
5
(
.79, N 9.47; found: C 32.87, H 5.84, N 9.57. UV–vis
–
1
–1
λmax, nm): 461 (ε = 16 (mol/L) cm ).
(
Caution! Transition-metal perchlorates are known to be
After washing with water and further addition of CHCl , the
3
hazardous and must be treated with care, especially in the
presence of organic solvents.
solution was dried (Na SO ), filtered, and the solvent re-
2
4
moved yielding an orange-brown oil that was dried under
high vacuum overnight. The cyclised diamide, 4,8-dimethyl-
1
,4,8,11-tetraaza-17-oxabicyclo[9.5.3]nonadecane-2,9-dione
Crystallography
(
5), solidified as a yellow, crispy honeycomb that was quite
+
hygroscopic. Yield: 2.0 g, 90%. MS: 327 (M + 1) .
The crude diamide 5 (2.5 g, 10.46 mmol) was transferred
to a 1 L flask using dry, freshly distilled THF (170 mL). Af-
[Co(L2)(Cl)](ClO4)2
X-ray quality crystals were grown by slow evaporation of
an aqueous solution containing the complex and NaClO4.
The experimental parameters for the complex are listed in
Table 1.
A crystal of dimensions 0.10 mm × 0.15 mm × 0.40 mm
was mounted in a glass Lindemann tube and optically cen-
tred in an Enraf-Nonius CAD-4 diffractometer employing
graphite-monochromated MoKα radiation. The unit cell was
refined by using 24 reflections in the 2θ range 25°–33°. The
diffraction data were collected using the ω/2θ scan mode. A
total of 3554 reflections were collected. The structure solu-
tion and refinement were completed using the PC version of
ter addition of the BH ·THF complex (340 mL, 1 mol/L),
3
the solution was refluxed for 24 h and cooled to room tem-
perature. The solution was cooled in ice water to quench the
remaining borane. Evaporation to dryness in vacuo gave a
cream-coloured solid to which was added 6 mol/L HCl
(
140 mL), and this solution was heated to reflux for 3 h.
Cooling in ice followed by the addition of KOH pellets to
pH ~ 14 and extraction with CHCl , and filtration, gave a
pale-yellow solution of the macrobicycle L . Upon drying
under high vacuum, a yellow oil formed. The product after
3
3
3
T. Rodopoulos. Unpublished observations.
M. Rodopoulos. Unpublished observations.
4
©
2005 NRC Canada