164
A. Facchinetti et al. / Inorganica Chimica Acta 324 (2001) 162–172
ene, chlorinated solvents, but is apparently well soluble
in ethyl acetate, ethyl acetoacetate, nitromethane,
DMF, DMSO.
2.2.7. [Cu(dipyam)(mta)(dcp)] (II)
(i) Hot equimolecular solutions of K(dcp) (1 mmol in
5 ml of methanol) and Cu(dipyam)(mta)NO3·H2O (0.43
g, 1 mmol, in 40 ml of methanol) were mixed and
stirred for 90 min. Compound II was separated from
the brown mother solution as a powder. Yield: 0.332 g,
66.1%. IR (KBr, cm−1): 1653 m; 1594 s; 1578 s, sh;
1534 m; 1473 s, 1453 s, 1434 s, sh; 1370 m, br; 1301
mw; 1240 mw; 1169 w, 1158 m; 1070, 1054 w; 1024,
1015 w; 906, 892, 879 w; 852, 832 w; 771 s; 733 m; 650
w; 624 w; 534 w; 455 w; 430 w, sh.
(ii) A solution of [Cu(dipyam)(dcp)2] (1.2 g, 2 mmol)
in 50 ml of dichloroethane was treated with some drops
of CH3COOH (2 N) in the same solvent, till the starting
brown color changed to green, and an equal volume of
diethyl ether was added to the clear filtrate. The
product, separated as a light brown powder after some
days in a refrigerator, was filtered off, washed repeat-
edly with water and dried in vacuo.
The product is sparingly or not at all soluble in
water, ether, acetonitrile, nitromethane; soluble in
methanol, hot acetone, toluene, ethyl acetate and ethyl
acetoacetate.
(ii) A suspension of [Cu(dipyam)(mta)Br] (0.126 g,
0.300 mmol) and Ag(dcp) (0.081 g, 0.300 mmol) in 50
ml of methanol was stirred for l h. The solid residue
was filtered off and the crystals of II were formed by
concentration of the filtrate.
2.2.5. Cu(dipyam)(OOCC6H5)(dcp)
(i) A method analogous to that of Section 2.2.2 was
followed, obtaining also in this case a blackish solution,
which became green after evaporation in the air. The
first solid precipitated, Cu(dipyam)(dcp)2, was filtered
out. The mother liquor, concentrated near dryness,
gave needles of the title compound. IR (KBr, cm−1):
1654 m; 1600, 1587 m, 1561 m, 1533 mw, 1479 s; 1442
w, 1433 mw; 1377 m, br; 1283 mw; 1234 mw; 1156 m;
1066 w; 1022, 1014 mw; 847 m; 768 ms, br; 732 w, 715
m; 686 w; 538 w; 440, 428 w, br.
2.2.8. Cu(dipyam)(mtn)(dcp) (III)
A
hot methanol suspension (50 ml) of Cu-
(dipyam)(mtn)Br (0.48 g, 1 mmol) and Ag(dcp) (0.27 g,
1 mmol) was stirred for 2 h, giving a dark red solution
and a solid mixture of AgBr and a green compound.
The solid component, filtered off, was dried and then
extracted with hot dichloromethane. The extracts were
added to the mother liquor and gave, after evaporation
and addition of ethylacetate, the product as a powder.
IR (KBr, cm−1): 1652 m, br; 1602, 1587 ms; 1570 w;
1546 w; 1532 mw; 1478 s, sh; 1432, sh, mw; 1397, 1382
w; 1351 mw; 1286 mw; 1234 mw; 1159 m, sh; 1124 w;
1071 m; 1013 mw; 881 w; 854 m; 763 ms, sh; 730 m; 648
w; 580 w; 537 w; 489 w; 425 mw.
At room temperature the product is insoluble in
water and ether, sparingly soluble in acetone, methanol
and ethanol, well soluble in pyridine; in hot solvents it
is slightly soluble also in toluene, ethyl acetate and
acetonitrile.
(ii) Solid Ag(dcp) (0.090 g, 0.333 mmol) was added to
0.143 g (0.328 mmol) of Cu(dipyam)(OOCC6H5)Br in
50 ml of hot methanol. The reaction was immediate,
with the formation of AgBr, which was filtered out
after half an hour of moderate heating. A high concen-
tration of the filtrate gave the complex as a powder.
The complex is insoluble in water, acetone, ethylac-
etate, methanol, ethanol, ether, acetonitrile, toluene;
moderately soluble in hot dichloromethane, chloroform
and DCE.
2.2.6. Cu(dipyam)(cmb)(dcp)
A suspension of 0.144 g (0.279 mmol) of Cu-
(dipyam)(cmb)Br and 0.076 g (0.282 mmol) of Ag(dcp)
in 60 ml of methanol was allowed to react under
stirring and mild heating. When the starting reagents
disappeared, the reaction mixture was filtered to elimi-
nate the precipitated AgBr and the deep brown filtrate
was left for evaporation. Black crystals (deep green
laminar aggregates at microscope) deposited.
IR (KBr, cm−1): 1658 m; 1600 w, 1588 m; 1565, 1535
m; 1486 s; 1452 s, 1430 m; 1388, 1366 m; 1302 w, 1285
w; 1238 mw: 1168, 1160 m; 1107 w; 1064 w, br; 1038,
1018 w; 814 sh, 804 mw; 770 ms; 740 mw, 725 sh; 634
w, br; 547, 532 w; 445, 426 w.
The product is insoluble in water, ether, acetone,
ethylacetate; very little soluble in hot methanol and
n-PrOH; moderately soluble in acetonitrile, benzene,
chlorinated solvents, methanol. It could be recrystal-
lized unchanged from dichloromethane/ether or
pyridine/ether.
2.2.9. [Cu(dipyam)(cmb)(tcp)] (IV)
A yellow–orange dispersion of 0.30 g (0.986 mmol)
of Ag(tcp) in 20 ml of methanol was added, under
stirring and mild heating, to a green suspension of
[Cu(dipyam)(cmb)Br] complex (0.50 g, 0.97 mmol) in
50 ml of the same solvent. The mother liquor changed
immediately to a dark brown color and the reagents
disappeared in a few minutes, with contemporaneous
formation of a mixture of AgBr and a bluish solid.
After half an hour the mixture was filtered and the
filtrate reduced by heating to about a quarter of the
starting volume. Needles, suitable for X-ray diffraction,
were separated by resting at room temperature. Addi-
tional amount of product was obtained by extraction
with methanol of the first solid residue. IR (KBr,
cm−1): 1659 m; 1600 w, 1588 m; 1569 mw; 1537 mw;