Cobalt(11) and zinc(11) complexes of the tripod' ligand

Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13

tris(2-benzimidazylmethy1)amine.Some five-coordinate
derivatives and some with mixed stereochemistriesl
K . THOMPSON,~
LAURENCE BARATHAM
S. RAMASWAMY,
A N D ELIZABETH
A. SEYMOUR
Depnrtmer~tof Cl~ernisrry,Mernoritrl Urti~versityof Nenfofoundlnt?d,St. Jolzr~'s,Nflcl., Caniidtr A l C 5 S 7
Received August 10, 1976

LAURENCE K. THOMPSON, BARATHAM S. RAMASWAMY, and ELIZABETH A. SEYMOUR. Can. J.

Chem. 55, 878 (1977).
A series of cobalt(I1) and zinc(I1) complexes of the title ligand are reported which contain
mixed stereochemistries, e.g., five-coordinate trigonal bipyramidal cations [M(ligand)XIt,
and four-coordinate anions, [MX,I2- (M = Co, Zn; X = C1, Br, NCS). The blue cobalt
complexes, [Co(ligand)X],[CoX,], are readily converted to purple five-coordinate complexes,
[Co(ligand)X]X, by recrystallisation from a solvent containing water, e.g. acetone. Other five-
coordinate cobalt and zinc derivatives were also prepared, [Co(ligand)X]X (X = NOs, CIO,),
[Co(ligand)X]BPh, (X = Cl, Br, NCS, NO,, ClO,), [Zn(ligand)X]BPh, (X = C1, Br, I, NCS).
Nuclear magnetic resonance data for all the zinc con~plexesindicate a significant deshielding of
one benzene ring proton on each coordinated benzimidazole group. Conductance data suggest
the possibility of cationic association through pseudo-hydrogen bonding in both the cobalt and
zinc derivatives involving C1, Br, NCS anions.
For personal use only.

LAURENCE K. THOMPSON, BARATHAM S. RAMASWAMY et ELIZABETH A. SEYMOUR. Can. J.

Chem. 55, 878 (1977).
On rapporte la prkparation d'une serie de conlplexes du cobalt(I1) et du zinc(I1) contenant
le ligand mentionne dans le titre et qui contiennent des stertochimies mixtes; par exemple des
cations bipyramidaux trigonaux pentacoordonnes [M(ligand)X]+ et des anions tttracoordonnes
[MX,I2- (M = Co, Zn: X = C1, Br, NCS). Les complexes bleus du cobalt, [Co(ligand)Xl2-
[Cox,], se transforment facilement en complexes pentacoordonnts violets [Co(ligand)X]X, par
recristallisation a partir d'un solvant contenant de l'eau, par exemple I'acCtone. D'autres derives
pentacoordonnes du cobalt et du cuivre ont aussi etC prepares: [Co(ligand)X]X (X = NO3,
CIO,), [Co(ligand)X]RPh, (X = C1, Br, NCS, NO,, CIO,) et [Zn(ligand)X]BPh, (X = C1, Br,
I , NCS). Les donnkes de rmn pour tous les conipiexes du zinc indiquent qu'il y a un deblindage
important d'un proton du noyau benzenique de chacun des groupes benzimidazole qui a ttC
coordonne. Les donnkes de conductivite suggerent la possibilite d'une association cationique,
par l'intermediaire d'un pseudo pont hydrogene dans les derives du cobalt ainsi que du zinc,
qui impliquerait les anions C1, Br, NCS.
[Traduit par le journal]

Introduction of o-phenylenediamine with nitrilotriacetonitrile

The coordinating ability of a number of
monodentate benzimidazole derivatives has
been reported in the literature (1-6). However,
examples of polyfunctional benzimidazole deriv-
atives and their complexes appear to be lacking.
We report here the synthesis and characteriza-
tion of a trisbenzimidazole derivative, tris(2-
benzimidazylmethyl)amine, which contains four
potential donor sites (Fig. 1, ligand abbreviated
NTB) and a number of its cobalt and zinc com-
plexes. The ligand has been synthesized by two
independent routes, one involving condensation
IPresented in part at the 56th Canadian Chemical
Conference of the Chemical Institute of Canada,
Montreal, June 1973.
=To whom correspondence should be addressed.
and the other by condensation of the diamine
with nitrilotriacetic acid (Fig. 1).
Reaction of the ligand with cobalt and zinc
salts, MX, (M = Co, Zn; X = C1, Br, NCS) in
ethyl alcohol led to the formation of ionic
derivatives, [M(NTB)X],[MX,], containing five-
coordinate pseudo-trigonal bipyramidal cations
and a four-coordinate tetrahedral anion. The
blue cobalt complexes appear to be stable in
fairly dry non-aqueous solvents but on re-
crystallization from aqueous acetone a series of
purple five-coordinate derivatives, [Co(NTB)-
X]X (X = C1, Br, NCS) were formed. These
trigonal bipyramidal cations could also be
stabilized as their tetraphenylborate salts by
direct synthesis from alcoholic solution. Other
 THOMPSON ET AL.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13
A 2 0 0 -C
FIG.1. Synthesis of tris(2-benzimidazylmethyl)amine.
five-coordinate derivatives include pink cobalt
nitrate and perchlorate derivatives, [Co(NTB)-
X]X, [Co(NTB)X]BPh, (X = NO,, ClO,) and
a series of white zinc complexes, [Zn(NTB)X]-
BPh, (X = Cl, Br, I, NCS). Structural assign-
ments have been justified by electronic, vibra-
tional, and nmr spectra and by conductance and
For personal use only.
magnetic data.
Experimental
Nuclear magnetic resonance data were obtained in
deuterated DMSO with Varian Associates A60 and
EM360 Spectrometers using SiMe, as internal calibrant.
Electronic spectra were recorded using Beckman DK2A
and Cary 17 Spectrometers and infrared data using
Perkin-Elmer models 457 and 283. Magnetic suscepti-
bilities were obtained by the Faraday method at room
temperature using a Cahn model -7600 coupled to a Cahn
gram electrobalance and conductivity data were obtained
using a General Radio Company bridge with impedance
comparator and a constant temperature bath adjusted
to 25 "C. Microanalyses were carried out by the Beller
laboratories, Gottingen, W. Germany and by Chema-
lytics, Tempe, Arizona. Metal analyses were determined
by Atomic Absorption using a Varian Techtron AA-5,
after prior digestion of the samples in concentrated HCl
or ternary solution (HNO,, H 2 S 0 4 , HC1O4 in a ratio
of 10: 1 :4 respectively).
Tris(2-benzimidazylmethy1)arnine (NTB)
Method A
Nitrilotriacetonitrile (5.0 g, 0.037 mol) and o-phenyl-
enediamine (12.0 g, 0.11 mol) were finely ground, mixed,
and heated together using a n oil bath at 200-210 "C.
When evolution of ammonia was essentially complete
(approx. 24 h) the cooled solid was crushed to a fine
powder, washed with ether, and extracted into methanol
and refluxed with decolourizing charcoal. After filtration
the methanol solution was reduced in volume to give a
creamy crystalline product (10.0 g, 66% yield) which was
recrystallized from methanol and dried thoroughly under
vacuum (mp 271 "C). Vacuum drying of the product
appears to be essential since nmr data indicate the
presence of solvate molecules (e.g., methanol, ethanol) in
NTB
the undried product, in a ratio of 1 :3, (ligand(solvent),).
These solvate molecules are probably hydrogen bonded,
one to each imidazole ring.
Method B
Nitrilotriacetic acid (15.3g, 0.0800mol) and o-
phenylenediamine (27.0 g, 0.250 mol) were finely ground
and heated together at 190-200 'C for 1 h using an oil
bath. The reaction mixture was cooled and crushed, and
refluxed in methanol containing decolourizing charcoal.
The solution was filtered hot and its volume reduced until
on cooling pinkish white crystals were obtained (17.5 g,
54% yield). Recrystallization was effected using methanol
and the product dried under vacuum (mp 270 "C). Anal.
calcd. for CZ4HZ1N7:C 70.8, H 5.16, N 24.1; found: C
70.5, H 5.21, N 23.5. Infrared spectrum (Nujol mull)
3140 (vNH), 1622, 1588 (vCN) cm-'; nmr (DMSO-d,)
relative intensity)) 12.1(8.5) (broad singlet, NH),
7.60(17), 7.19(17) (AA'BB' multiplet, aromatic CH),
4.12(17) (CH,); mass spectrum, major mass peaks
(m/e(relative intensities)) 407(3) P, 277(15), 276(80),
248(8), 146(57), 133(10), 132(96), 131(100), 119(24),
104(22), 92(9), 77(24).
Metal Complexes of NTB
Cortiplexes of Mixed Stereochemistry .'M(NTB) X i2-
IMX,]
Stoichiometric amounts of the metal salt, MX,
(hydrated or anhydrous) (M = Co, Z n ; X = Cl, Br,
NCS) and NTB were dissolved separately in hot absolute
ethanol and the hot solutions mixed with stirring for
about 112 h. In some cases the products crystallized from
the hot solution while in others reduction in volume
followed by cooling was necessary to induce crystalliza-
tion. The products were recrystallized from absolute
ethanol and dried under vacuum at 90 OC.
Five-coordinate Conlplexes
iCoiNTB) X j X (X = CI, BY,NCS)
The blue cobalt complexes of mixed stereochemistry
were found to be hydrolytically unstable in aqueous
solvents and on recrystallization from aqueous acetone
(approx. 10% H 2 0 ) purple complexes of formula [Co-
(NTB)X]X were produced. The compounds were dried
under vacuum at 90 OC.
[Co(NTB) XjBPh, ( X = CI, BY,NCS, NO3, C1O4)
A hot ethanolic solution of the ligand and a slight
 880 CAN. J . CHEM. VOL. 55. 1977

1. Analytical and other data

TABLE
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13

Found Calcd M
yo --
Compound Colour yield C H N C H N Found Calcd

Blue
Blue
Blue
Purple
Purple
Purple
Purple
Purple
Purple
Pink
Pink
Pink
Pink
White
White
White
White
White
White
White
For personal use only.

exsess of sodium tetraphenylborate was added with
stirring to a hot ethanolic solution of a stoichiometric
amount of the cobalt salt. On cooling purple (X = C1,
Br, NCS) and pink (X = NO,, C10,) products were
obtained which were recrystallized from ethanol and
dried under vacuum at 90 "C.
The chloro-, bromo-, and isothiocyanato compounds
were also synthesized by adding ethanolic NaBPh, to an
ethanolic solution of [Co(NTB)X]X.
Zn(NTB)X--BPh, ( X = CI, BY, I, NCS)
These complexes were prepared in a similar fashion to
the analogous cobalt derivatives.
[Co(NTB)X--X ( X = NO3, C10,)
Stoichiometric amounts of the cobalt salt and NTB were
mixed in hot ethanol to give pink solutions from which
pink crystalline solids were obtained. The products were
recrystallized from acetone and dried under vacuum at
90 "C.
Analytical and other data for these systems are given
in Table 1.
Results and Discussion
Characterization of tile Ligand
Our interest in this ligand, which to our
knowledge has not been previously reported in
the literature. stemmed in Dart from our earlier
involvement with ligands containing imidazoline
rings (7) ~ h i c hwere obtained by simple con-
densation of dinitriles lvith dianlines, e.g.,
ethylenediamine, A simple extension of this
reaction to the trinitrile, nitrilotriacetonitrile, led
to the title ligand vdhich appeared to have the
right geometrical features to be a stereo-
chemically selective 'tripod' ligand capable of
forcing metal ions to adopt predominantly one
stereochemistry, i.e., a distorted trigonal bi-
pyramid.
2-Substituted benzimidazoles have been pre-
pared in good yield by the reaction of o-phenyl-
enediamine with monobasic acids (e.g. formic,
propionic, acetic, etc.) under reflux in dilute
hydrochloric acid. Extension of this reaction to
dibasic acids, e . g . oxalic and malonic, did not
lead to 2-substituted benzimidazoles, but with
succinic acid both mono and bis-2-benzimida-
zole derivatives were produced (8, 9). Hein and
co-workers (10) prepared 2-alkyl and -aryl
benzimidazole derivatives by the high tempera-
ture (250°C) condensation of acids, esters,
amides, or nitriles with an appropriate diamine
in the presence of polyphosphoric acid which
acts both as a catalyst and a solvent. Both of
these methods were tried for the preparation of
NTB but with little success. A much better
method proved to be the direct fusion of nitrilo-
triacetonitrile or nitrilotriacetic acid with o-
phenylenediamine at high temperatures, followed
by recrystallization from methanol (Fig. 1). The
products obtained by both synthetic routes were
identical in all respects as indicated by analysis,
melting point, infrared, nmr, and mass spectros-
 THOMPSON ET AL.
copy. An attempted degradation of NTB using
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13
conc. HCl was carried out under reflux. NTB
did not degrade but simply formed its hydro-
chloride salt from which NTB was regenerated
on treatment with base.
In the nmr spectrum of the ligand thc methy-
lene protons are all equivalent, appearing as a
singlet shifted downfield slightly in comparison
with nitrilotriacetonitrile, while the aromatic
protons appear as a symmetrical set of peaks
typical of the AA'BB' spectrum observed for
symmetrically ovtho-disubstituted benzene rings,
e.g., o-phenylenediamine, naphthalene, benzi-
midazole, etc. (Table 5). The symmetrical nature
of this set of peaks indicates a plane of symmetry
bisecting each benzimidazole unit and passing
through the 2-carbon atom. This suggests that
the imidazole ring proton is delocalized equally
along the N-C-N framework. This proton
appears as a very broad resonance at 12.1 o.As
will be shown later, the symmetry or lack of
For personal use only.
symmetry associated with this set of nmr peaks
indicates whether or not the benzimidazole rings
are coordinated.
The infrared spectrum of NTB is similar to
that of benzimidazole itself.
C/zaracrerizatio~zof tlze Complexes
Complexes of the general formula [M(NTB)-
X],[MX,] (M = Co, Zn; X = C1, Br, NCS),
[M(NTB)X]X (M = Co; X = CI, Br, NCS,
NO,, ClO,), and [M(NTB)X]BPh, (M = Co;
X = C1, Br, NCS, NO,, ClO,; M = Zn;
X = CI, Br, I, NCS) were obtained. These
complexes bear some resemblance to previously
reported systems involving tetradentate tripod
ligands. Sacconi and co-workers (1 1-13) have
recently reported five-coordinate cobalt and
nickel complexes of potentially tetradentate
tripod ligands based on triethylamine with a P
position on each ethyl group replaced by a donor
group, e.g., N, 0 , P, As. The bulkiness of the
coordinating groups appeared to be a factor in
directing the stereochemistry of the resulting
complexes, e.g., with decreasing bulkiness of the
donor groups a trend towards six-coordination
was observed. In addition complexes were cited
where the ligand behaved as a bidentate or
terdentate. In terms of the chromophoric en-
vironment of the ligand, NTB, it bears more
resemblance to trenMe (tris(2-dimethylamino-
ethyl)amine) which acts as a tetradentate tripod
881
ligand, forming pseudo-trigonal bipyramidal
systems (14). NTB appears to be the first example
of a tetradentate tripod ligand involving three
coordinating benzimidazole groups.
Cobalt Complexes
The tetraphenylborate ion is a good non-
coordinating anion which has been used effec-
tively to stabilize five-coordinate cations. Re-
action of NTB with cobalt salts in ethanol, in
the presence of one equivalent of sodium tetra-
phenylborate, produces a series of complexes
[Co(NTB)X]BPh, (X = Cl, Br, NCS, NO,,
C10,) (Table 1). Electronic spectral data for
these salts are given in Table 2. The solid mull
transmittance and acetone solution spectra are
very similar indicating a similar metal ion
stereochemistry both in the solid state and in
solution. The spectral band positions and their
intensities are not typical of either octahedral or
tetrahedral cobalt(I1) but they bear a close re-
semblance to previously reported spectra for
pseudo-trigonal bipyramidal cobalt derivatives
containing tetradentate tripod ligands (Figs. 2,
3) (1 1-14).
Recent studies by Bertini and co-workers (15)
have attempted to simulate observed spectra of
some pseudo-trigonal bipyramidal cobalt(1I)
complexes using both the crystal field and angular
overlap approach. Using a C,, field good agree-
ment was obtained between calculated and ob-
served transition energies for the chromophores
CoNN,Br (NN, = trenMe), CoNS,Br (NS, =
tris(2-tert-buty1thioethyl)amine) and CoNP,Br
(NP, = tris(2-diphenylphosphinoethy1)amine).
Four major transitions are observed in these
systems assigned from the 4A, ground state in
C, symmetry. A iow energy band around 5-6
kK, assigned to 4 E c 4A2, appears to be largely
unaffected by structural variations whereas
tetrahedral distortion tends to shift the other
4E + 4242 and the P t F transitiolls to lower
four bands: 4~ -
energy. The main features of the spectra include
,A2 (5-6 kK), t ,A2 (10-
12 kK), 4A2(P) + 4.A2(14-16 kK), 4E(P) + 4 A z
(17.5-19.5 kK).
The spectra of the tetraphenylborate NTB
derivatives exhibit absorptions in three main
areas; 5.2-6.8 kK, 10.5-13.3 kK, 16.7-20,s kK.
The lower energy band shows little fine structure
in solution but in the solid state splitting of the
band is observed in some cases, which is en-
 882 CAN. J. CHEM. VOL. 55. 1977

TABLE
2. Electronic spectra (an-')*
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13

(a) [Co(NTB)XIt

Compound 4EC---- ,A2 c-----~A~ 4E(P) t---- 4A2f

[Co(NTB)Br]Br

[Co(NTB)Br]BPh,

[Co(NTB)Br], [CoBr,]

[Co(NTB)(NCS)]NCS.H20

[Co(NTB)(NCS)]BPh,

[CO(NTB)(NCS)I~[C~(NCS),~
For personal use only.

Compound
,T,(F) t---- ,Az
(~2)
(b) [c0x412-

,T1(P) - (~3)
4A2

[Co(NTB)CI], [CoCI,] u 6100(145) 6700(136) 14500(480) 15200(480) 16000(363) 16750(726)

b 5200 5600 6300 14600 [16000] 17200
[Co(NTB)BrI2[CoBr,] a 5600(150) 14300(775) 15000(467) 15700(300)
b 5200 5800 14300
[CO(NTB)(NCS)]~[C~(NCS),~a 6950(403) 8300(260) 16150(1980) 16600(1910) 17100(1920)
b 6900 7500 8500 16700
"Labels mean tlie foliofilng: a , solution in acetone; b, mull transmittance spectrum (room temperature); c , solution in nitromethane. [ I
shoulder, (

?The 'A2(P) -
molar extinction coefficient. Some bands have been assigned mice, i.e. to both five-coordinate and tetrahedral cobalt(l1). These
bands probably contain oberlapping components associated kith both stereochemistries.
4.'12 transition appears to be missii~yin aln~ostall the spectra %ith the exception of [Co(NTB)CIlCI and [Co(NTB)CIlBPh4
where a weak shoulder at 16000 cm-1 can possibly be assisned to thls transition.

hanced at low temperature (77 K). The high
energy band is split into two conlponents in
most cases, especially in solution. The splitting
of this band has been observed in some other
trigonal bipyramidal systems and can possibly
be associated with spin-orbit effects or deviations
from C,, symmetry. In the NTB complex ions
the ligand is assumed to be acting as a tetra-
dentate in an approximately C,, syminetry en-
vironmerlt (Fig. 4) and the observed spectral
bands are tentatively assigned as follows: 4E c
4A2 (5.2-6.8 kK), 4 E +- 4 ~ (10.5-13.3
2 kK), and
"E(P) c "A, (two components 16.7-20.5 kK)
(Table 2). (The QA,(P) +- 4 ~ ,transition is
probably hidden beneath the band envelope
associated with 4E(P) c Q 2 ; see footnote T,
Table 2.)
Magnetic data (Table 3) indicate that these
complexes are high spin, typical of systems of
this type with hard donor atoms (16). The
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13
FIG.2. Electronic spectra of some NTB complexes.
A. Mull transmittance spectrum of [Co(NTB)(NCS)]BPh,
(arbitrary absorbance). B, C. [Co(NTB)(NCS)jNCS and
[Co(NTB)(NCS)]BPh,, respectively, in acetone.
For personal use only.
Acetone Solution
FIG. 3. Acetone solution spectra to illustrate the
presence of [CoBr412- and [Co(NTB)Br]+ in the cobalt
bromide colnplex of mixed stereochemistry. The chloro-
and isothiocyanato analogues exhibit similar spectra
which indicate the presence of four-coordinate anions
and five-coordinate cations. A , [Co(NTB)BriBr: 23,
6nucleophil~creactibity constant' established by
Sacconi (16) for the donor set N,X (X = C1,
Br, NCSj lies :n the range i 5 4-1 9.1, typ~calof
h ~ g hspln system>. The magnetic moments for
FIG. 4. Stereochemistry of NTB complex.
the five-coordinate tetraphenylborate derivatives
fall in the range 4.3-4.7 BM. Moments for
typical trigonal bipyramidal systems with tripod
ligands containing N, 0 , S, P donor atoms fall
in the range 4.4-4.7 BM (1 1, 13, 14).
The tetraphenylborate complexes (X = C1,
Br, NCS) exhibit conductances (Table 3) which
are somewhat lower than would be expected for
1 : I electrolyte species (17). These data are
rather difficult to rationalize in the light of the
proposed nature of these species, which are
assumed to exist as five-coordinate cations
stabilized by the tetraphenylborate anion. How-
ever cationic association leading to large bulky
ions with low ion mobility and the low ion
mobility associated with BPh,- itself could lead
to significantly lower molar conductances than
would be expected. Cobalt complexes of tren-
(2,2',2"-triaminotriethylamine) of formula [Co2-
(tren),X,](BPh,), (X = OCN-, SCN-, C1-,
N,-) have recently been shown to contain five-
coordinate, outer sphere bridged cations, in
which the bridging association is thought to
occur via a hydrogen bond, Co-X----HN-Co
(18). This association leads to weak antiferro-
magnetic exchange between the cobalt centres.
Outer sphere association of this type could
possibly exist in the NTB complexes via the
imidazole ring hydrogen, which is likely to
reside on the non-coordinating ring nitrogen
atom.
A concentration dependence of the molar con-
ductance of [Co(NTB)Br]BPh, in nitromethane
was studied in the range lQ-3-lQ-s A4 at 25 "C
(Table 3). A, was found to be 75.9 and the slope
of the Kohlrausch plot (A, - A, rs. ,/?) was
found to be 960. A typical slope for a 1: 1
electrolyte is around 200 (slope for NaBPh, in
MeNO, = 216 (19)) and it is evident that
cationic association is occurring in solution. One
possible associative mechanism could involve
pseudo-hydrogen bonding, as suggested pre-
viously, of an axial halogen (or pseudo-hal-
ogen) on one ion with one of the three imi-
dazole hydrogen atoms on another to form
a species of the type {[Co(NTB)Br],,)"'. It
 C A N . .I.CHEM. VOL. 5 5 . 1977

TABLE
3. Magnetic moment and conductance data
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13

P (BM)
Abr*
Compound (mho mol-' cm2) Solid? Solution$
For personal use only.

*Solvent nitromethane at approx. AM(25 'C).

?Magnetic moment per metal measured in solid state by Faraday method.
tMagnetic moment measured in CHCI,I(CH3),C0(4A CHCI,) by nmr method (22 and ref'erences therein).

seems likely that the other cobalt halide and
thiocyanate derivatives would behave similarly
in nitromethane. Further studies on the con-
centration dependence of the conductivity of
these systems are being carried out. However,
additional support for an associative interaction
of this type is apparent when one considers the
molar conductance values which follow the
order NCS > Br > C1, in keeping with the
electronegativities associated with these co-
ordinated anions. Also the strong association
that exists between NTB and alcohols (a 1 : 3
solvate is formed on recrystailization from, e.g.,
methanol or ethanol which required prolonged
drying under vacuum to desolvate) lends support
to an associative effect of a hydrogen bonding
type in the NTB complexes.
The purple complexes [Co(NTB)X]X (X =
C1, Br, NCS) have magnetic moments (Table 3)
typical or' high spin systems and electronic
spectra which are identical to their tetraphenyl-
borate analogues both in solution and in the
solid state (Fig. 2). This indicates that these
species contain pseudo-trigonal bipyramidal
cations, apparently stabilized by a negative ion
capable of coordination. Spectral assignments for
these five-coordinate cations are assumed to be
the same as those for the tetraphenylborate
analogues (Table 2).
Conductivity data in nitromethane (Table 3)
indicate species with some ionic character and
low values again suggest the possibility of
cationic association involving N-H---X bridges.
This is supported by the conductance values
which follom~ the order NCS > Br > CI. An
alternative explanation for the low conductance
values for these systems results from a considera-
tion of solution equilibria involving the forma-
tion of e.g. neutral four- or six-coordinate
species :
In the octahedral case NTB mould act as a
tetradentate, while in the tetrahedral case it
would presumably act as a bidentate ligand.
Electronic spectra of nitromethane solutions of
these coinplexes do not show the presence of
bands attributable to tetrahedral or octahedral
species but are the same as the spectra obtained
in acetone.
The pink nitrate and perchlorate complexes,
[Co(NTB)X]X (X = NO,, CIO,), have elec-
tronic spectra (Table 2) which are almost
identical to their tetraphenylborate analogues.
 THOMPSOh ET AL.
their three main absorptioi~bands occurring at
slightly higher energies than the corresponding
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13
chloro, bromo, and isothiocyanato derivatives.
It seems reasonable to suppose that these com-
pounds contain trigonal bipyramidai cations
each with one coordinated nitrate and perchlor-
ate group. Magnetic data for these systems also
appear to be consistent with five-coordinate,
trigonal bipyrainidal cobalt(1I).
Conductivity data for the nitrato derivatives
in nitromethane (Table 3) suggest the presence
of 1 : 1 electrolytes. The bisperchlorato derivative
appears t o be a 1 : 2 electrolyte, which is rather
surprising since it implies displacement of a co-
ordinated perchlorate group by a nitromethane
molecule. The tetraphenylborate analogue ex-
hibits a lower inolar conductance which could
possibly be associated with a 1 : 2 electrolyte in
the presence of a large bulky ion like BPh,-.
The electronic spectra of nitromethane solutions
of [Co(NTB)(ClO,)]Cl0, and [Co(NTB)(CIO,)]-
BPh, are almost identical, but differ somewhat
For personal use only.
in terms of transition energies (Table 2) from
their corresponding acetone spectra., suggesting
possible axial involvement of a solvent n~olecule.
The deep blbie complexes [Co(NTB)X],-
[COX,] (X = GI, B r , NCS) exhibit electronic
spectra (Fig. 3) (Table 2) which show un-
equivocally the presence of tetrahedral [CoX,I2-
anions and five-coordinate cations identical to
those present in the purple complexes [Co(NTB)-
X]X and [Co(NTB)X]BPh,. In each case a !: 1
correspondence is observed between the peaks
associated with the [CoX,I2- anions in the blue
complexes and the salts [rz-Bu,N][CoX,] run in
the same solvent. Magnetic data (Table 3)
indicate high spin systems but the moments are
slightly lower than would be expected. The ob-
served moment should represent an average for
the three nietal centres in the con~plexand an
average momelit based on two five-coordinate
cations (Table 3) and e.g. CoCI,'-, shot~ldbe
around 4.4 B M . The low observed moments
could indicate the presence of cationic associa-
tion in the solid slate, e.g. of the hydrogen bond-
ing type (1 8), leading to weak antiferromagnetic
exchange.
The thiocyanate complex exlllbits a molar
conductance close to the range expected for a 1 : 2
eleclro!yte, while the lower values of rhe chloride
and bromide complexes are perhaps more
typical of 1 : 1 eiectro!ytes. Again the conductalzce
885
order follows the sequence NCS > Br > C1
suggesting a hydrogen bonding association be-
tween cations. These conductivity data are
paralleled by the analogous zinc compIexes
[Zn(NTB)X],[ZnX,]. A comparison of the
solution (CEI,NO,, (CH,),CO) and solid elec-
tronic spectra of these mixed stereochelnistry
systems suggests that the same species exist both
in the solid state and in solution.
Zinc Con~ylexes
Two series of zinc complexes were obtained:
(Zn(NTB)X],[ZnX,] (X = G1, Br, NCS) and
[Zn(NTB)X]BPh, (X = C1, Br, I, NCS). The
former are thought to be analogous to the
cobalt con~plexes of mixed stereochemistry,
containing two five-coordinate cations and a
four-coordinate, tetrahedral anion. The tetra-
phenylborate salts are assumed to contain
trigonal bipyramidal cations. Conductivity data
in nitromethane (Table 3) indicate ionic species,
but again low values suggest the possible exist-
ence of associative effects.
Nuclear magnetic resonance data obtained in
DMSO-d6 (Table 5) indicate that the ligand is
acting as a quadridentate and lies on a threefold
axis of symmetry within each complex cation.
The methylene proton resonance occurs as a
singlet in each case, indicating equivalent
methylene protons, which are shifted downfield
slightly (12-18 Hz) with respect to the free
ligand. NTB exhibits a very symmetrical set of
aromatic proton resonances (AA'BB') indicative
of a plane of symmetry within each benzimida-
zole group. Jn all the complexes the aromatic
proton resonances are observed in two groups of
lines (Fig. 5 ) . Three protons remain at essentially
the same chemical shift observed for the free
ligand, while one proton of the lower field pair
is shifted downfield considerably. It is assumed
that the benzene ring protons nearest to the
imidazole ring are the more deshielded and would
be observed at lower field, corresponding to the
lower field half of the aromatic proton reson-
ances observed for NTB. On coordination one
of these protons, which is sti!l coupled to the
other ring protons, is shifted downfield by some
70-80 Hz. This significant dov~nfieldshift cor-
responds to a marked deshielding of one ring
proton witl-I respect to the others.
One obvious coni;!~sionto draw from the lack
of symmetry of the benzene ring proton reson-
 CAN. J. CHEM. VOL. 55. 1977
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13
For personal use only.
FIG.5. Nuclear inagnetic resonance spectra in DMSO-
d,. A, NTB; B, [Zn(NTB)Br]BF, (the tetrafluoroborate
complex was used because of interfering peaks associated
with the corresponding tetraphenylborate complex); C,
[Zn(NTB)Br],[ZnBr,].
ances would be the coordination of one imida-
zole nitrogen to a zinc ion. In addition, since
only one set of benzimidazole proton resonances
appear in the spectrum, it is assumed that all
three benzimidazole groups are involved in co-
ordination to the same metal. The slight down-
field shift associated with the methylene protons
suggests coordination of the apical nitrogen also.
Models suggest that an essentially strain free
way for the ligand to coordinate to a metal ion
would be as a tripod ligand, with the apical
nitrogen occupying an axial site and a nitrogen
atom from each benzimidazole group occupying
a trigonai equatorial site in a pseudo-trigonal
bipyramidal structure. In this configuration one
a proton in each benzene ring lies close to the
other axial site which contains an electronegative
group, e.g. C1, Br, NCS. The close proximity of
this electronegative group to the a ring proton
could be responsible for a through space
electronic interaction leading to a deshielding
effect and a downfield shift of the a proton.
Alternative, but perhaps less likely, explanations
would be an electron withdrawing effect, trans-
mitted from the axial anionic group via the metal
through five bonds or from a neighbouring
hydrogen bonded ion in an associated structure,
if such association exists in highly polar di-
methylsulfoxide.
Infrared Data
The infrared spectra of the NTB complexes
studied were in general fairly complex and did
not provide very much structurally useful in-
formation. This was especially true in the far
infrared where interfering bands associated with
the ligand itself prevented any definitive struc-
tural assignments.
Infrared spectra of the nitrate derivatives
contain bands that can be assigned to ionic and
monodentate nitrate groups. The bisnitrato
derivative exhibits bands at 846, 1390, and 700
cm-I (Table 4) which can be associated with an
ionic nitrate, and are absent in the tetraphenyl-
borate analogue. Both compounds exhibit bands
around 980 and 1310 cm- ' assigned to A , modes
associated with a monodentate nitrate group
(20). In the case of the perchlorate derivatives it
is possible to pick out a strong doublet (1050,
1130 cm-I for [Co(NTB)(ClO,)jCIO,; 1050,
1140 cm-' for [Co(NTB)(ClO,)]BPh,) due to
the v,(T,) vibration in a tetrahedral species like
CIO,- which is split into A , + E o n lowering the
symmetry from T, to C,,. This suggests the
 THOMPSON ET AL.

TABLE4. Infrared data (cm-')

(a) Thiocyanato derivatives
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13

Compound v(CN)[NCS]

(b) Nitrato derivatives

\
NO3 - 0

Compound v2(Azf') v3(Ef) v4(EJ) A1 AI

(c) Perchlorato derivatives

For personal use only.

/
M-0-Cl-0
\
0
c10,- -
Compound v3(T2) E AI

*KBr disc spectra. All other data obtained using mulls in either Nujol or
hexachlorobutadiene.

TABLE5. Nuclear magnetic resonance data (ppm in DMSO-d6)*

6H01 6HC2 6Hh 6CH2 6NH

Compound (m) ( 4 (m) (s) (bs)
NTB 7.60
[Zn(NTB)CI]2[ZnC14] 8.79
[Zn(NTB)BrI2[ZnBr,] 8.89
[Zn(NTB)(NCS)],[Zn(NCS),] 8.69
[Zn(NTB)C1]BPh4.H20 8.67
[Zn(NTB)Br]BPh,.H,O 8.70
[Zn(NTB)I]BPh, 8.76
[Zn(NTB)(NCS)]BPh, 8.!2
[Zn(NTB)CI]BF, 8.64
[Zn(NTB)Br]BF, 8.77
*m = mult~plet,s == singlet, bs = broad singlet, nd = not detected. The Ha and H, protons appear as
asymmetric complex multiplets which appear to contain five major components, one of x+hichhas relatively
low inteilsity, In estimating the chemical shifts associated nith these protons the centre of gra>ity of the four
higher intensity components was determined in each case.
 CAN. J. CHEM. VOL. 5 5 , 1977

the free ligand suggested a more localized ring

structure in which the CN bond lengths were
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Scientific Library of Lomonosov Moscow State Univ on 12/24/13

different. By analogy with the imidazoline com-

plexes the nitrato and perchlorato derivatives
possibly have more localized ring structures
FIG.6. n, Localized ring structure; h, deiocalized ring (Fig. 6a) while the other complexes possibly have
structure. more delocalized ring structures (Fig. 6b). Also
it is assumed that in the NTB complexes the
presence of a coordinated perchlorate group in imidazole ring is coordinated to the metal via
both cases. The bisperchlorato derivative ex- the tertiary ring nitrogen atom (Fig. 6).
hibits a strong singlet at 11 10 cm-', which is
assigned to the v,(T,) stretching vibration in an Aeknowledgennents
ionic perchlorate group (20). We are indebted to the National Research
The thiocyanate complexes exhibit bands Council of Canada for financial support for this
associated with C N stretch in the range 2039- work and in particular for the purchase of the
2097 cm-' (Table 4). For the complexes [M- Cary 17 Spectrometer. Also we wish to express
(NTB)(NCS>l2[M(NCS),1 (M = Co, Zn) the our gratitude to Greg Mawhinney of this de-
higher energy band is assigned to N-bonded partment for obtaining a large proportion of the
thiocyanate in the complex cation, while the conductance data.
lower energy band is associated with N-bonded 1 . D. M. L. GOODG.IME.M. GOODG.AME. and G. W .
thiocyanate in the anion [M(NCS),]'- (M = Co, RAYNERC~NH Inorg.
~ M .Chim. Acta.6(2), 245(1972).
Zn). The tetraphenylborate complexes exhibit a 2. M. V . ARTEAIENKO and E. A. CHISTGAKOVA. Ukr.
For personal use only.

Khim. Zh. 37.978 (1971).

single C N stretch which is associated with N- 3. S. P. GHOSHand A. MISHRA.J . Inorg. Nucl. C h e n ~ .
bonded thiocyanate, whiie for the complex 33.4199 (1971).
[Co(NTB)(NCS)]NCS.H,O the higher energy 4. M. V. A R T E ~ I E N KK. O .F. S L Y L S . \ R E ~ KandO . D. A.
band is assigned to N-bonded thiocyanate and SI-AKHOV. Ukr. Khim. Zh. 38, 227 (1972).
5 . M. V. .~RTEMESKO. K . F. SLYUSARENKO. and D. A.
the lower energy band to ionic thiocyanate (21). ST.+KHOV. Zh. Ncorg. Khim. 17(1). 164 (1972).
NTB exhibits two absorptions at 1622 and 6. M. J . M. C . ~ M P B E LD. L .W. CARD.R. G m ~ s ~ o w 1 . 4 ~ .
1588 cm-' which are assumed to be due to C N and M. GOLDSTEIN. J . Chem. Soc. Dalton. 1687
stretch in the imidazole ring. The con~plexesall (1972).
7. A. B.P. LEVER.B.S. R A M ~ S W A M S.YH.. SIMOYSEN
exhibit the same two bands; the lower energy and L. K. T H O ~ I P SCan. O ~ . J. Chem. 48.3076 (1970).
band falling in the range 1590-1607 cm-', while 8. M. 4. PHILLIPS. J. Chem. Soc. 172 (1928).
the higher energy band falls in the range 1610- 9. M. A. PHILLIPS. J . Chem. Soc. 2393 (1928).
1632 cin-'. In most cases, with. the exception of 10. D. W. HEIN.R. J. ALHEIM,and J. J. LEAVITT. J. Am.
the nltrate and perchlorate complexes, the higher Chem. Soc. 79.427 (1957).
11. L. S.4cco.u.i and R . MOR-ISSI.J. Chem. Soc. A, 575
energy band lies belov~its counterpart in the (1970).
free ligand, ivhile the lower energy band occurs 12. R.MORASSIand L. SACCONI. J . Chem. Soc. A, 492
above 1588 cm-' in all cases. The close similarity (1971).
of a11 the complexes in this spectral region sug- 13. R.M O R A Sand ~ I L. S ~ G C G N J . IChem.
. Soc. A. 1487
gests a similar coordination environment around 14. (1971). M. CIAMPOLINI and N. NARDI.Inorg. Chem. 5, 41
the metal in all cases and the behaviour of the (1966).
ligand as a tetradentate. 15. I. BERTINI. D. GATIFESCHI. and A. SCOZZAFAVA. In-
A previous study on the cobalt and nickel org. Chem. 14,812 (1975).
16. L. SACCONI. J. Chem. Soc. A, 248 (1970).
complexes of some bidentate imidazoline ligands 17. W. J. GEARY. Coord. Chem. Rev. 7,81 (1971).
( 7 ) related the C N stretching frequency in the 18. D. MICHAEL DUGG-\Uand D . w r ~N . HENDRICKSOY.
imidazoline rings to the state of localization Inorg. Chem. 14. 1944 (1975).
along the NCN ring framework. As expected, 19. R. D. FELTHAMand R. 6 . HAYTER.J. Chem. Soc.
X-ray data confirmed the coordination of the 20. 4587 (1964).
K ~ i z u ONAKAMOTO. Infrared spectra of inorganic and
imidazoline ring via the tertiary nitrogen, but coordination compounds. 2nd ed. Wiley-Interscience,
also suggested two possible structural types New York. 1970.
based on C N bond lengths. A C N frequency 21. E. KONIG and K . MADGEJA.Inorg. Chem. 6 , 48
below that of the free ligand indicated a de- (1967).
R R.SCHEFFOLD.
22. J. L ~ J - I G Eand J . Chem. Ed. 9, 646
localized imidazoline ring, with essentially equal (1972); DAVIDOSTFELDand IRWINA. COHEN.J.
C N bond lengths while frequencies higher than Chem. Ed. 12,829 (1972).