PolyhedronVol. 15, No. 20, pp.

3617 3622, 1996

Copyright ,'~, 1996 Elsevmr Science Ltd
~ Pergamon Printed in Great Britain. All rights reserved
0277 5387/96 $15 00+0.00
S0277-5387(96)00081-2

COORDINATION O F N I C K E L A N D C O B A L T W I T H N-
MORPHOLINE OR N,N-DIETHYL, N'-MONOSUBSTITUTED
BENZOYL THIOUREAS

ISABELLE DI~CHAMPS-OLIVIER, EMMANUEL GUILLON, AMINOU

MOHAMADOU and JEAN-PIERRE BARBIER*
GRECI, Laboratoire de Chimie Min6rale, Universit6 de Reims Champagne Ardenne,
B.P. 1039, 51687 Reims Cedex 2, France

(Received 26 October 1995: accepted 26 January 1996)

Abstraet--A series of N-morpholine or N,N-diethyl, N'-substituted benzoyl thioureas

(R = C1, Br, OMe or NO2 in ortho-, meta- or para-position) has been synthesized by
condensation of morpholine or diethylamine with substituted benzoyl isothiocyanates.
NMR spectra and magnetic measurements have shown square-planar NiL2 and fae-CoL 3
complexes. The influence of the different substituents on the NMR and electronic spectra
was studied. Copyright 9 1996 Elsevier Science Ltd

In previous papers, we have reported on the coor-
dination of copper, nickel and cobalt with N,N-
disubstituted, N'-benzoyl thioureas. We have
shown that the nitrogen substituents do not affect
the nature and the geometry of these compounds 1
and that the redox properties of copper complexes
are influenced by the benzoyl substituents. 2
We report here on the coordination of nickel
and cobalt with N,N-diethyl or morpholine, N'-
substituted benzoyl thioureas (morph-R-btu-H) to
show the influence of the benzoyl substituents (elec-
tronic effect, steric constraints, etc.) on these met-
allic complexes
S 0
Only three ligands (morph-R-btu-H with R = p-
C1, p-OMe and p-NO2) have been described in the
literature. 3
EXPERIMENTAL
All spectroscopic and microanalytical measure-
ments have been described previously, l An LC-
10AS Shimadzu liquid chromatograph with an
SPD-10A Shimadzu UV-Vis detector (254 nm) was
used to separate the isomers. The Rosyl 5/~m col-
umn was 150 mm long and had a diameter of 4.6
mm. The complexes (1 mg cm -3 in a 70-30 hexane-
ethylacetate mixture) were eluted with a flow rate of
1 cm3 min -1. The ligands were prepared as before2
by condensation of the substituted benzoyl iso-
thiocyanates with the morpholine or the diethyl-
amine.

R = CI, Br, OCH3 or NO2 in ortho, meta and

Synthesis of the complexes
para position

The metallic acetate was added dropwise to the

R1 = R2 = C2H5, Et2 R - b t u - H ligand, in a 1:2 molar ratio for nickel and 1:3
RI, R2 N = O ~q-- ,morph-R-btu H
ratio for cobalt, in methanol. The crude solids were
recrystallized in methylene chloride, some drops of
methanol induce crystallization. The solid com-
plexes were dried at room temperature in vacuo (ca
* Author to whom correspondenceshould be addressed. 10 mm Hg).
3617
3618 I. DI~CHAMPS-OLIVIER et al.
R E S U L T S AND D I S C U S S I O N
Analytical data for the complexes are given in
Table 1. We note that the cobalt complexes analyses
are not always very satisfactory. In these cases,
N M R and IR spectra show the presence of solvent
crystallization molecules. Thermogravimetric
curves present a loss of solvent up to 200~ and
then, practically without step, the decomposition of
the complex. Consequently, the drying conditions
are difficult to determine: this could explain why
the experimental C, H, N percentages are a little
lower than the calculated values. The strong steric
constraints generated by the morpholine and the
ortho-substituent of the benzoyl group prevent the
formation of CoL 3 complexes.
The diamagnetism of all the complexes indicates
clearly a square-planar geometry for nickel and a
complete oxidation of cobalt(II) to the octahedral
cobalt(Ill). Some cobalt(II) complexes can be
obtained under nitrogen after fast addition of
cobalt acetate and fast filtration. The Co(morph-p-
Br-btu)2 compound (Found: C, 40.1; H, 3.3; N,
7.8. Calc. C, 40.3; H, 3.3; N, 7.6%) has been
isolated. Its magnetic moment (4.46 B.M.) and the
visible spectrum in the solid state are characteristic
of a tetrahedral geometry. However, solution stud-
ies were not possible because the cobalt(II) was
oxidized to cobalt(Ill) even in an inert atmosphere.
Electronic spectra
The UV absorption spectra exhibited a very
broad band in the 200-300 nm range. Gaussian
deconvolution was performed using an application
developed under " Q U A T T R O P R O " by J. Rim-
bault in our laboratory. Five absorption bands were
2.50
A
2.00
1.50
1.00
0.50
0.00 k i
20000 30000
Fig. 1. UV spectra of Ni(Eh-o-Br-btu)2 c = 5 10 -4 mol dm 3 in
*Experimental spectra.
required to fill the spectral envelope in the UV
region and three in the visible. An example is given
in Fig. 1. For the ligand, we have obtained four
strong bands assigned to the rc ~ re* transition of
the benzoyl group and a fifth weaker (e ,,~ 50
m o l - ~dm 3 c m - 1) band assigned to the n --* re* tran-
sition of carbonyl. 4 All the substituents on the aro-
matic ring generate a bathochromic effect. The
effect is weaker with an attractive group such as
NO2 (ca + 10 nm) and stronger with a substituent
with donor character (O-CH3 : ca + 30 nm). In the
metallic complexes, all the n --* re* intraligand bands
are shifted to higher wavelength (ca 10 nm). The
n--* n* ligand transition is masked by a stronger
band which depends on the metal; these n ~ n*
transitions probably involve metal and ligand
orbitals.
In the visible region, the cobalt complexes show
two transitions ; a band at 621 + 2 nm for the meta-
and para- derivatives and at 6 1 4 + 2 nm for the
ortho-derivative and a shoulder at 472 + 2 nm for
all the compounds (Fig. 2). These values agree with
an octahedral geometry with a $303 chromo-
phore, sa Moreover, the fact that the transition
around 620 nm appears symmetrical is indicative
that the distortion from the Oh symmetry is slight.
In the case of nickel complexes (Fig. 3), we have
obtained a weak band around 615 nm and a strong
one at 514_ 2 nm for ortho- and para-derivatives
and 508 + 2 nm for the meta-derivative, charac-
teristic of square-planar geometry. 5b
N M R spectra
Proton N M R data are given in Table 2 for the
N,N-diethyl derivatives with an electron donor or
40000 c m -1 50000
CH2C12, cell length = 1 mm.
 Table 1. Analytical and physical data"

Compounds M.p. C H N V(c=o) Compounds M.p. C H N V{c=o)

(':C) % % % (cm -~) CC) % % % (cm -~)

Ni(morph-o-Cl-btu)2 216 46.1 3.4 8.8 1520 Co(morph-o-Cl-btu)3 . . . . .

Ni(morph-m-Cl-btu)2 289 46.1 3.4 8.8 1516 Co(morph-m-Cl-btu)3 190 47.0 3.7 9.0 1517
Ni(morph-p-Cl-btu)2 298 45.6 3.4 8.8 1515 Co(morph-p-Cl-btu)3 218 47.3 3.8 8.8 1514
(46.0) (3.9) (8.9) (47.3) (3.9) (9.2)
Ni(Et2-o-Cl-btu)2 140 47.8 4.2 9.2 1526 Co(Et2-o-Cl-btu)3 144 49.9 4.6 9.6 1526
(3
Ni(Et2-m-Cl-btu)2 144 48.3 4.7 9.3 1524 Co(Et2-m-Cl-btu)3 133 49.9 4.5 9.6 1524 9
O
Ni(Et2-p-Cl-btu)2 212 48.1 4.6 9.2 1523 Co(Et2-p-Cl-btu)3~ 204 49.7 4.6 9.2 1523
(48.2) (4.7) (9.4) (49.8) (4.9) (9.7)
Ni(morph-o-Br-btu)2 218 40.2 3.0 7.7 1521 Co(morph-o-Br-btu)3 -- --
O
Ni (morph-m- Br-btu) 2 295 39.8 2.7 7.6 1519 Co (morph-m-Br-btu) 3 213 40.8 3.3 7.4 1512
Ni(morph-p-Br-btu)2 294 39.4 3.0 7.5 1520 Co(morph-p-Br-btu)3 229 40.6 3.3 7.6 1512 O

(40.3) (3.4) (7.8) (41.4) (3.4) (8.0) z

Ni(Et2-o-Br-btu)2 158 41.9 3.7 7.9 1527 Co(Et2-o-Br-btu)3 104 42.2 3.7 7.9 1525
Ni(Et2-m-Br-btu): 153 41.6 3.7 8.0 1527 Co(Et2-m-Br-btu)3 134 43.2 3.8 8.2 1522 e'~

Ni(Et_,-p-Br-btu)2 227 42.0 3.8 8.0 1520 Co(Et2-p-Br-btu)3 b 167 42.3 3.7 7.7 1520 O
(41.9) (4.1) (8.1) (43.2) (4.2) (8.4)
Ni(morph-o-OMe-btu)2 . . . . Co(morph-o-OMe-btu)3 . . . . .
Ni (morph-m-OM e-btu)_, 245 50.6 4.5 8.9 1521 Co(morph-m-OMe-btu)3 225 51.8 4.7 9.3 1518
Ni(morph-p-OMe-btu)2 274 50.0 4.6 8.9 1508 Co(morph-p-OMe-btu)3 240 52.0 4.7 9.4 1510
e-*
(50.6) (4.9) (9.1) (52.2) (5.0) (9.4)
Ni(Et2-o-OMe-btu)2 113 52.8 5.7 9.3 1518 Co(Et2-o-OMe-btu)3 . . . .
Ni(Et2-m-OMe-btu)2 122 52.9 5.9 9.4 1519 Co(Et2-m-OMe-btu)3 155 54.9 5.9 9.7 1519
O"
Ni(Et2-p-OMe-btu)2 173 52.8 5.6 9.5 1512 Co(Et2-p-OMe-btu)3 ~ 182 54.5 5.7 9.7 1514 t~

(53.0) (5.8) (9.5) (54.8) (6.0) (9.7) N

O
Ni(morph-o-NO2-btu)2 292 44.3 3.4 12.8 1530 Co(morph-o-NO2btu)_~ . . . .
Ni(morph-m-NO2-btu)2 314 43.6 3.5 12.6 1525 Co(morph-m-NO2btu)3 193 44.4 3.6 12.4 1533
Ni(morph-p-NO2-btu)2 315 44.8 3.5 12.7 1530 Co(morph-p-NOzbtu)3 225 45.6 4.3 13.5 1533 =
(44.5) (3.7) (13.0) (45.9) (3.8) (13.4) P,
Ni(Et2-o-NO2-btu)2 225 46.5 4.1 13.4 1530 Co(Etz-o-NO2-btu)3 144 47.8 4.5 13.4 1531
Ni(Etz-m-NO2-btu)2 241 46.5 4.1 13.4 1527 Co(Et2-m-NO2-btu)3 184 47.8 4.6 13.7 1530
Ni(Et2-p-NOe-btu)2 264 45.7 4.2 13.1 1533 Co(Et2-p-NO2-btu)3 208 47.6 4.5 13.7 1535
(46.5) (4.6) (13.6) (48.0) (4.7) (14.0)
Ni(morph-p-OEt-btu)2 254 52.0 5.3 8.6 1506 Co(morph-p-OEt-btu)3 223 53.5 5.3 8.8 1511
(52.1) (5.3) (8.7) (53.7) (5.4) (8.9)
Ni(Et.,-p-OEt-btu)2 155 55.0 6.2 8.8 1512 Co(Et2-p-OEt-btu)3 217 55.9 6.3 9.3 1516
(54.5) (6.2) (9.1) (56.2) (6.4) (9.4)

Calculated values are given in parentheses.

bAnalytical data after elimination of crystallization solvent by thermogravimetry.
3620 I. D t ~ C H A M P S - O L I V I E R et al.
0.35
A
0.30

0.25

0.20

0.15

0.10

0.05

0.00
10000 14000 18000 r m-1" 22000
Fig. 2. Visible s p e c t r a o f C o ( E t 2 - o - B r - b t u ) 3 c -- 5 10 -4 m o l d m -3 in CH2C12, cell l e n g t h = 1 c m .
* E x p e r i m e n t a l spectra.

0.12

A
0.10

0.08

0.06

0.04

0.02

0.00 ~ ,----- I
10000 14000 18000 r m - 1 22000
Fig. 3. Visible s p e c t r a o f N i ( E t z - o - B r - b t u ) 2 c = 5 10 * m o l d m -3 in CH2C12, cell l e n g t h = 1 c m .
9Experimental spectra.

attractor group as benzoyl substituents. The chemi-
cal shifts of the aromatic ring protons increase with
the electron-withdrawing character of the sub-
stituents and can be arranged in the order 6Uar,,with
OMe < 6H~yt with C1--~ 6 H without substituent
< 6Hary,with Br < 6n,ry,with NO2. The complexation
always induces a shift to higher field (0.15 ppm
decreasing) for the 3-, 4- and 5-positions. However,
with meta- and para-derivatives, we observed an
opposite effect for the 2-,6-positions ; the chemical
shift increasing (+0.40 ppm for the OMe deriva-
tive) decreases with the electron-withdrawing
power of the substituent.
Except for the ortho-nitro derivatives, the meth-
ylene proton resonance of the R1, R2 ethyl group
presents two signals around 3.6 and 4.0 ppm.
Irradiation at 3.6 or 4.0 ppm shows clearly that the
two ethyl groups are non-equivalent, probably due
to the restricted rotation about the thiocarbonyl-
nitrogen bond. The complexation modifies the nat-
ure and the anisotropic effect of the carbon-sulphur
bond which leads to the coalescence of the two
- C H 2- signals and the sharpening of the methyl
resonance.
As we have shown in previous work I for unsym-
metrical bidentate ligands, a single resonance for
the proton is indicative of fat compounds. Thefac-
configuration of all the complexes studied was con-
firmed by the 13C N M R data. The presence of one
peak in the chromatogram was indicative of the
 T a b l e 2. IH N M R d a t a for the ligands, nickel(II) a n d c o b a l t ( I I I ) c o m p o u n d s
p a H 2 3

NyN~4
O S 6 5

3N H 82 33 3.~ 65 36 3~ 311 ~OCH3

o
Et:-o-NO2-btu L 8.15, s, I H 8.10, s, 1H 7.65, m, IH 7.65, m, 1H 7.75, d, 1H 3.90, b, 4H 1.35, t, 6H O
Ni 7.85, d, 2H 7.55, m, 2H 7.50, m, 2H 7.45, m, 2H 3.60, q, 4H 1.15, t, 6H
3.70, q, 4H 1.25, t, 6H
Co 8.00, d, 3H 7.55, m, 3H 7.50, m, 3H 7.45, d, 3H 3.65, m, 6H 1.15, t, 9H O
3.95, q, 6H 1.30, t, 9H
Et2-o-OMe-btu L 10.05, s, 1H 7.05, d, 1H 7.10, t, 1H 7.55, t, I H 8.15, d, I H 3.65, b, 2H 1.35, b, 6H 4.05, s, 3H
4.05, b, 2H .z
Ni 6.85, d, 2H 6.85, t, 2H 7.30, t, 2H 7.75, d, 2H 3.75, m, 8H 1.25, t, 6H 3.75, s, 6H
1.35, t, 6H
Et:-m-NO2-btu L 8.50, s, 1H 8.70, s, 1H 8.40, d, 1H 7.70, t, I H 8.20, d, IH 3.65, b, 2H 1.35, b, 6H
o
4.00, b, 2H
Ni 9.00, s, 2H 8.50, d, 2H 7.65, t, 2H 8.35, d, 2H 3.80, q, 4H 1.30, t, 12H
3.85, q, 4H
Co 8.95, s, 3H 8.45, d, 3H 7.45, t, 3H 8.25, d, 3H 3.85, m, 12H 1.30, t, 9H
1.25, t, 9H
Et2-m-OMe-btu L 8.25, s, 1H 7.40, d, 1H 7.40, m, 1H 7.10, m, 1H 7.40, d, 1H 3.65, b, 2H 1.30, b, 6H 3.85, s, 3H
4.05, b, 2H
Ni 7.75, s, 2H 7.05, d, 2H 7.25, m, 2H 7.70, m, 2H 3.75, q, 4 H 1.25, t, 6H 3.85, s, 6H g
3.80, q, 4H 1.30, t, 6H
N
Co 7.75, s, 3H 6.95, d, 3H 7.20, t, 3H 7.80, d, 3H 3.85, m, 12H 1.25, t, 18H 3.60, s, 9H O
Et2-p-NO2-btu L 8.75, s, 1H 8.35, d, 1H 8.05, d, 1H 8.05, d, 1H 8.35, d, 1H 3.65, b, 2H 1.30, b, 6H
4.05, b, 2H
Ni 8.25, s, 2H 8.25, s, 2H 8.25, s, 2H 8.25, s, 2H 3.80, m, 8H 1.25, t, 6H
1.35, t, 6H p~
Co 8.30, d, 3H 8.15, d, 3H 8.15, d, 3H 8.30, d, 3H 3.85, m, 12H 1.20, t, 9H
1.25, t, 9H
Et2-p-OMe-btu L 8.10, s, 1H 7.80, d, 1H 6.95, d, 1H 6.95, d, 1H 7.80, d, 1H 3.60, b, 2H 1.30, b, 6H 3.85, s, 3H
4.05, b, 2H
Ni 8.05, d, 2H 6.85, d, 2H 6.85, d, 2H 8.05, d, 2H 3.75, m, 8H 1.25, t, 6H 3.85, s, 6H
1.30, t, 6H
Co 8.15, d, 3H 6.80, d, 3H 6.80, d, 3H 8.15, d, 3H 3.85, m, 12H 1.15, t, 9H 3.85, s, 9H
1.25, t, 9H

s : singlet ; d : d o u b l e t ; t : triplet ; q : quadruplet ; m : multiplet ; b : broad.

b,-)
3622 I. DI~,CHAMPS-OLIVIER et al.
presence of only one isomer; the isomeric purity of
thefac products always being better than 98%.
Unfortunately, the N M R spectra do not dis-
tinguish between the two possible square-planar
isomers in the case of the nickel compounds.
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1. A. Mohamadou, I. D6champs-Olivier and J. P. Barb-
ier, Polyhedron 1994, 13, 1363.
2. A. Mohamadou, I. D6champs-Olivier and J. P. Barb-
ier, Polyhedron 1994, 13, 3277.
3. J. C. Brindley, J. M. Caldwell, G. D. Meakins, S. J.
Plackett and S. J. Price, J. Chem. Soc., Perkin Trans.
I 1987, 1153.
4. N. L. Allinger, M. P. Cava, D. C. De Jongh, C. R.
Johnson, N. A. Lebel and C. L. Stevens, Chimie
Organique, French Edn, Vol. 3, p. 834. McGraw-Hill,
Paris (1976).
5. A. B. P. Lever, Inorganic Electronic Spectroscopy, 2nd
Edn. Elsevier, Amsterdam (1984) (a) p. 463; (b) p.
535.