INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, VOL.

VI, 133-142 (1974)

Kinetics of Reactions of Schiff Base

Complexes of Iron(I1). V. Reactions of
the Complex of the Hexadentate Ligand
NN"'-Bis-[- -( 8-pyridy1)benzylidene]- triethyl-
~

enetetramine in Acid Solution and with

Hydroxide, Cyanide, and Peroxodisulphate

E. R. GARDNER AND F. M. MEKHAIL

School of Chemistry, Leicester Polytechnic, Leicester LEI 9BH, England
AND
J. BURGESS
Department of Chemistry, University of Leicester, Leicester LEI 7RH, England

Abstract
The preparation and characterization of the iron(I1) complex of the hexadentate
Schiff base ligand NN"'-bis-[cr-(2-pyridyl)benzylidene]triethylenetetramine are reported.
Kinetic patterns and rate constants for aquation of this complex, and for its reactions with
hydroxide, cyanide, and peroxodisulphate have been determined. Activation parameters
for the reaction with cyanide, in aqueous solution, are A H : = 24.3 kcal/mole and AS: =
+ 1 cal/deg-mole.

1. Introduction
The preparation, and the kinetics of substitution and of peroxodisulphate
oxidation, of tris-Schiff base complexes of iron( 11) containing bidentate ligands of
formula (I) have been extensively studied [ 1-51. We were interested in examining
the reactivity of iron(I1) complexes of similar Schiff bases of denticity higher than
two, and decided to try to synthesize a hexadentate analogue of formulation I
and determine the kinetics of some reactions of the iron(I1) complex of such a
ligand. In the present paper we report the preparation of the iron(I1) complex
of the hexadentate Schiff base derived from phenyl 2-pyridyl ketone and triethyl-
enetetramine, and the kinetics of the reactions of this complex in acid solution
133

0 1 9 7 4 by John Wiley & Sons, Inc.

134 GARDNER, MEKHAIL, AND BURGESS

and in solutions containing hydroxide, cyanide, and peroxodisulphate.

R = H or Ph
X = range of substituents
I

2. Experimental
The method used resembled that established earlier [2, 3, 51 for the prepara-
tion of iron(I1) complexes of bidentate Schiff bases I. 2.0 g AnalaR iron(I1)
ammonium sulphate was dissolved in 10 ml water; 7.3 ml triethylenetetramine
was added. After thorough mixing, a solution of 9.3 g phenyl 2-pyridyl ketone
in 10 ml methanol was added. The mixture was left overnight at room temper-
ature, during which time an intense dark blue color developed. The product
solution was filtered, and the iron(I1) complex of the hexadentate Schiff base
ligand (hxsb) NN”’-bis-[a-(2-pyridyl)benzylidene]triethylenetetramine(formula-
tion 11) was precipitated by the addition of aqueous sodium perchlorate solution.
The product analyzed thus: C = 48.9%, H = 4.6%, N = 11.9%; the formula
[Fe(C30H32NS)1(C104)2 requires C = 49.3%, H = 4.4%, N = 11.5%. The visible
absorption spectrum of a solution of the complex showed one broad band, vmax =
16450 cm-’ with molar extinction coefficient 7560.
The kinetics of the reactions studied were monitored spectrophotometrically,
using 1 cm silica cells in the thermostatted cell compartment of a Unicam SP800
spectrophotometer. The fastest runs were initiated by ejecting the contents of
thermostatted syringes through a simple mixing device into the cell in the spectro-
photometer cell holder. Concentrations of reactants and other experimental
conditions are specified in Tables 1-111. First-order rate constants and activation
parameters, with their standard errors, were computed (Elliott 4130) using a
standard least mean squares program.

3. Results and Discussion

The preparation and some properties of the iron(I1) complex of the hexa-
dentate Schiff base ligand (hxsb) NN”’-bis-[a-(2-pyridyl)benzylidene]triethylene-
tetramine (formulation 11) are described in Section 2. That this complex is
substitution inert and low spin is at first sight slightly surprising in view of the
presence of only two of the bipyridyl-like chelating units 111. Complexes with
the formulae Fe(LL)2X2are only low spin for X = CN, NCO [6], or S-bonded
sulphinate [7] when LL = bipyridyl (bipy), and for X = CN, NCO, or NO2 [6]
when LL = phenanthroline (phen). No stable complexes of the type
 REACTIONS OF SCHIFF BASE COMPLEXES 135

Fe(phen)2(NI-IJ22* or Fe(phen)z(en)'+are known, though the extra metal-

ligand interaction when (CN)2 replaces phen is reflected in the existence of the
low-spin complex Fe(CK)4(en)2- [8]. Schiff base ligands (sb) of the type I form
iron( 11) complexes Fe(sb)32i which are slightly less stable than Fe(phen)3*+ [4],
so a low-spin complex Fe(sb)2LAZ2+ with L = an aliphatic nitrogen ligand, seems
unlikely. O u r isolation of the low-spin iron(I1) complex of an equivalent
hexadentate Schiff base ligand therefore provides yet another illustration of the
importance of the chelate effect in stabilizing complexes. In the present case, the
siting of the two aliphatic ligating nitrogen atoms in the middle of the molecule
may be significant, for with such an arrangement the hexadentate ligand is
eficimtly anchored by the two terminal N-C---C- N units (formula-
tion 111).

I1 111

A. Aquation
I11 acidic aqueous solution the complex Fe(hxsb) '+is converted into aquated
iron(I1) and protonated ligand molecules; the initial intense blue color of the
solution fades completely:
(1) Fe(hxsb)?+ + nII+ + Fe2+.aq + hxsbI-I,"'
The kinetics of this reaction are, at a given acid concentration, first order to
beyond 80% of complete reaction. Observed first-order rate constants for
aquation in acid solution (always in the presence of a large excess of acid) vary

'rABLE I. First-order rate constants k for aquation of the iron(I1)-hexadentate

Schiff base complex in aqueous hydrochloric acid, ionic strength 0.333M
(maintained with sodium chloride), at 35.OoC. Initial [complex] 8 X 10-5M.
. . . . . . . . . . ............ .
. .... .... -~
....... -

[HClI/M lo5 k, sec-'

_.

0.066 0.35
0.099 0.59
0.132 0.93
0.198 1.78
0.231 2.13
0.264 2.50
0.297 2.89
0.333 3.30
......... _- .
. ~ ............--_ _- .. .-
136 GARDNER, MEKHAIL, A N D BURGESS

Figure 1. Comparison of the dependences of aquation rates k on acid concentration for

flexible multidentate ligand complexes of iron(I1). Ligands: A-hxsb; B-terpy; C-bipy.

with acid concentration (Table I).’ In general, rates of aquation of low-spin

iron(I1) complexes vary with acid concentration when the leaving ligand is
flexible, for example, 2,2‘-bipyridyl 191 or 2,2’,6’,2’’-terpyridyl [lo, 111, but are
independent of acid concentration when the leaving ligand is rigid, for example,
1,lO-phenanthroline [ 12].2 The behavior of Fe(hxsb)’+ conforms to this general
pattern.
The actual form of the dependence of aquation rates on acid concentration
for Fe(hxsb)*+ is compared diagrammatically with that for Fe(bipy)X2+and that
for Fe(terpy)22+ in Figure 1. Solubility difficulties have prevented us from
ascertaining whether the pH rate profile for Fe(hxsb)2+becomes parallel with the
acid concentration axis at high acid concentrations; the profile for Fe(terpy) 22+
only reaches this limiting state at acid concentrations above about 10 N [14]. At
lower acid concentrations, the p H rate profile for the aquation of Fe(hxsb)2+
resembles that of Fe(ter~y)2~+ rather than that of Fe(bipy)32+. The p H rate
profile for Fe(bipy)a2+ is interpreted by a reaction scheme involving intermediates
containing monodentate (formulation IV) and monodentate monoprotonated
(formulation V) bipyridyl ligands [ 151. The more complicated behavior reported
for Fe(terpy)22+and for Fe(hxsb)2+ requires the intermediacy of both mono-
dentate and bidentate (and perhaps higher denticities for the latter) ligand
species and their protonated derivatives. Extrapolation of the pH rate profiles
for the aquation of Fe(terpy)z2+ and of Fe(hxsb)2+ to zero acid concentration
(pH 7) indicates an extremely slow rate of ligand dissociation in neutral solution;

The standard errors of the experimentally determined rate constants in Tables 1-111 are
in the region of 2-3%.
2 Although if the rigid phenanthroline ligand has a substituent, for instance an amino group
which can be protonated, a dependence of aquation rates on acid concentration is observed [13].
 REACTIONS OF SCHIFF BASE COMPLEXES 137

this has been confirmed for the former complex by radiochemical monitoring of
ligand exchange [ 161.

IV V

B. Reaction with hydroxide

Fe(hxsb)?+ reacts with hydroxide ion in aqueous solution. I n the presence of
a large excess of hydroxide ion first-order kinetics are observed; the variation of
such observed first-order rate constants with hydroxide ion concentration is
reported in Table TI. A plot of these rate constants against hydroxide ion con-

TABLE 11. First-order rate constants k for reaction of the iron(I1)-hexadentate

Schiff base complex in aqueous sodium hydroxide solution, ionic strength 0.33313.1
(maintained with sodium chloride), at 35.0"C. Initial [complex] 8 X 10-5M.

[NaOH]/M lo5 k, sec-1

0.132 0.79
0.198 1.26
0.264 1.62
0.333 2.19
___

centration is, like the corresponding plots for this complex in acid solution and for
Fe(terpy)P [ l l ] , a gentle curve whose tangent increases as the hydroxide ion
concentration increases. The reaction of low-spin iron( 11) complexes with
hydroxide ion generalyy proceeds by parallel reaction paths of rate-determining
dissociation followed by rapid scavenging of iron(I1) species thus produced and of
rate-determining nucleophilic attack of hydroxide at the iron(I1) in the complex
[ 171; in the presence of oxygen the iron is eventually oxidized to iron(II1) species
[18]. Such a reaction scheme corresponds to a linear dependence of observed
first-order rate constants on hydroxide ion concentration (large excess) ; our obser-
vation of a curved dependence suggests that the reaction of Fe(hxsb)2+, as of
Fe(terpy)??+, in aqueous hydroxide, involves attack of hydroxide not only at the
hexadentate (bis-tridentate) initial complex, but also at one or more inter-
mediates of significant lifetime. Such intermediates are presumed to be com-
plexes containing penta- and perhaps tetra- (and lower) dentate ligands.
138 CARDNER, MEKHAIL, AND BURGESS

C . Reaction with cyanide

In the presence of a large excess of cyanide, Fe(hxsb)2+ reacts by a process
exhibiting first-order kinetics. T h e variation of observed first-order rate con-
stants with cyanide concentration is shown in Table 111 for aqueous solution and

TABLE
111. Observed first-order rate constants k and derived second-order rate constants kz
for reaction of the iron(I1)-hexadentate Schiff base complex with cyanide in aqueous
solution and in 50YO v/v aqueous ethanol, ionic strength of 0.333M (maintained
with potassium chloride). Initial {complex]8 X 10-5M.
Tem-
pera- 105k2,
Solvent ture, "C 105k,sec-1 I./mole sec

[CN-IIM 0.132 0.198 0.264 0.333

Water 25.3 0.24 0.31 0.37 0.43 0.94
35.1 0.54 0.77 1.10 1.30 3.9
37.6 0.61 0.97 1.30 1.45 4.3
39.7 1.02 1.43 1.86 2.28 6.3
45.5 1.55 2.57 3.33 4.65 15.1
[KCNIIM 0.066 0.132 0.165 0.231 0.264 0.297
50Yoethanol 25.3 0.65 1.41 1.50 2.4 2.5 2.9 9.6

for 50y0 aqueous ethanol. Plots of these sets of first-order constants against
cyanide concentrations3 were linear, passing within experimental uncertainty
through the origin. T h e simplest mechanism consistent with this kinetic pattern
is bimolecular cyanide attack at the iron(J1) center. However, it is conceivable
that a t high concentrations of cyanide ion such plots might begin to curve, even-
tually becoming parallel to the cyanide concentration axis. Such behavior would
betoken a limiting S N (or~ 0)reaction, with the intermediacy of a transient five-
coordinated iron(I1) species. In practice it is difficult to work at varying high
cyanide concentrations maintaining constant ionic strength. I n fact no evidence
has yet been obtained, either by us [ l , 20, 211 or by other workers [22], for an
S N(lim)
~ mechanism operating in what appear to be simple second-order reactions
of low-spin iron(I1) complexes with nucleophiles such as cyanide or imidazole.
We therefore believe that second-order rate constants (Table 111) calculated from
our kinetic results correspond to bimolecular cyanide attack a t the iron. From
the variation of these second-order rate constants with temperature we have calcu-
lated an activation enthalpy of 24.3 f 1.1 kcal/mole and an activation entropy
of + 1 & 3 cal/deg-mole. These activation parameters are similar to those

3 Concentrations of free cyanide in aqueous solution were calculated from known concentra-

tions and the known values of the pK of hydrocyanic acid as a function of temperature 1191; in
50% ethanol rate constants were plotted against the concentration of potassium cyanide added.
 REACTIONS OF SCHIFF BASE COMPLEXES 139

reporred for cyanide attack at, for example, Fe(bipy)s2+ 1201 and at F e ( ~ h e n ) ~ ~ +
P11.
The products of the reactions of complexes of the type Fe(LL)S2+, where
LL =: phen, bipy, or a bidentate Schiff base, with cyanide are mixed ligand
complexes Fe(LL)2(CN)2; further reactions to Fe(LL)(CN)42- and to Fe(CN)$-
are extremely slow [23]. We were therefore interested to determine whether
cyanide would displace the whole hexadentate ligand, or whether an intermediate
containing both cyanide and Schiff base ligand bonded to the iron would be the
first product. Such a species might be produced by the cyanide displacing one
N--- C--C- N unit (scheme 111) to produce scheme VI; displacement of
the two secondary aliphatic ligating nitrogens of VI by two more cyanide ions to
produce scheme VII might well be an easy process. Displacement of the two
secondary aliphatic nitrogens of Fe(hxsb)2+ before displacement of one of the
terminal units seems geometrically unlikely.

I #\I,
NC-F~-CN
NC’ I

VI VII

The product of the kinetic runs has a strong charge-transfer band in the visible
region; it is not Fe(CN)64- and may therefore be formulation VI or VII. We
have tried to isolate this “kinetic product” by using a variety of preparative
approaches derived from published methods for preparing compounds of the
type Fe(LL)2(CN)2 and Fe(LL)(CN)42-, where LL = bipy or phen. The claret-
co1ort:d solids produced always ’contain a large admixture of potassium cyanide
which cannot be removed by washing, since the solubility characteristics of our
“kinetic product’’ closely resemble those of potassium cyanide, i.e., very soluble
in water, moderately soluble in methanol, sparingly soluble in ethanol, and
insoluble in a variety of other organic solvents. While this unfortunate situation
prevents characterization by analysis, it does suggest, by analogy with
Fe(LlL)2(CN)2 and salts of Fe(LL)(CN)42-, that our product i s the salt of an
anionic species such as Fe(hxsb) (CN)42- (formulation VII) rather than uncharged
Fe(hxsb)(CN)z (formulation VI). Some support for the formulation of the
primary product of reaction of Fe(hxsb)2+with cyanide as scheme VII can be
derived from two aspects of the charge-transfer spectrum of this product. It is
known that the ratios of the molar extinction coefficients for the lowest energy iron
140 GARDNER, MEKHAIL, AND BURGESS

to LL charge-transfer band in the series of complexes Fe(LL)32+,Fe(LL)2(CN)2,

and Fe(LL)(CN)42- approximate to 3:2:1. The ratio for Fe(hxsb)2+ to our
product is 3: 1.1, which supports formualation VII rather than VI. The charge-
transfer spectra of compounds of the type cis-M(LL)z(L')Z and cis-M(LL)
are markedly solvent dependent [24]; the degree of solvent dependence, which can
be characterized [25] by the slope of a plot of frequencies of maximum absorption
against respective ET values [26], varies significantly with the nature of M, LL,
and L'. Thus, for a relevant example, the slope of such a plot for Fe(bipy)z(CN)z,
or an analogue containing a substituted phen ligand, lies between 7.7 and 8.6 X
kcal/mole, but for Kz[Fe(bipy)(CN)J the slope is only 3.8 X kcal/mole
[25]. Wave numbers of maximum absorption for our product have been plotted
against ET values for a range of mixed aqueous solvents (up to 80% acetone and
100% ethanol); the slope of the correlation line is 8 X lop3 kcal/mole, which is
much less than the values of 13.4 and 15.3 x 10-3 kcal/mole for the complex
Fe(LL)2(CN)2,where LL is an analogous Schiff base (formulation I) with R = Ph
and X = 3,4-diMe, in hydroxylic and nonhydroxylic solvents, respectively [25].
Again this provides some slight support for formulation VII rather than VI. We
are thus able to suggest only very tentatively that the product of the reaction of
Fe(hxsb) 2+ with cyanide under the conditions of our kinetic experiments is
Fe(hxsb)(CN) 42-, presumably with the hxsb ligand bidentate, bonding to the
iron by one N-C-C-N unit; our uncertainty as to the nature of the
product does not, however, affect our kinetic deductions concerning the attack of
cyanide at Fe(hxsb)2+.
D. Reaction with peroxodisulphate
The complex Fe(hxsb)2+ reacts relatively quickly with peroxodisulphate in
aqueous solution; the second-order constant at 25.0"C is approximately 5 l./mole-
sec. The redox potential, determined by potentiometric titration against
cerium(1V) in N acid, is 1.01 V a t 4°C. This low temperature was necessary in
order to minimize acid aquation of the complex during the course of the redox
potential determination. Assuming that dE"/dT for F e ( h ~ s b ) ~ +is / ~approxi-
+
mately equal to that for F e ( ~ h e n ) ~ ~ [27],
+ ' ~ +then the estimated redox potential
for the iron(I1)-iron(II1)-hexadentate Schiff base couple at 25.0"C is 1.03 V.
As we have stated before, we believe that peroxodisulphate oxidation of these
low-spin iron(I1) complexes is outersphere in mechanisms [28], [29]. We would
therefore expect a graph of logarithms of second-rate constants against the redox
potentials for the respective iron(I1)-iron(II1) complex couples to be linear [30].
Such a kinetic-redox potential correlation has been reported for peroxodisulphate
oxidation of the limited range of complexes Fe(bipy)s2+ and its 4,4'-diMebipy,
phen, and 5-Me phen analogues [31]. These observations were later confirmed
[29], but the additional results in the later work pertaining to Fe(5-C1 phen)s2+
and to Fe(5-N02phen)S2+ do not fit the correlation plot. We have plotted in
 REACTIONS OF SCHIFF BASE COMPLEXES 141

+1

+10

Figure 2. Attempted correlation of second-order rate constants k 2 for peroxodisulphate

oxidation of low-spin iron(I1) complexes with the redox potentials of the respective iron(I1)-
iron(II1) complex couples. Ligands: 1-hxsb; 2 4 , 7 - d i M e phen; 3-5,5'-diMe bipy; 4-
3,5,6,8-tetraMe phen; S b i p y ; 6-5-Me phen; 7-phen; 8-3-S03- phen; 9-5-N02 phen;
IO-5--SO3- phen; 1 I-ferrozine.

Figure 2 logarithms of rate constants for peroxodisulphate oxidation against

redox potentials for the respective iron(I1)-iron(II1) complex couples for (sub-
stituted) 1,lO-phenanthroline and 2,2'-bipyridyl ligands and for ferrozine and
the present hexadentate Schiff base complexes. We have omitted from this
figure the results for a few relevant compounds where there are large uncertainties
in one or the other rate constant for peroxodisulphate oxidation or the redox
potential. Thus, for example, it seems inappropriate to include Fe(terpy)P on
the graph as its reported redox potential varies between 0.93 V I321 and 1.25 V
[33]. Figure 2 does suggest a rough correlation of rate constants for peroxo-
disulphate oxidation with redox potentials for the bipyridyl and phenanthroline
ligands. Some of the scatter might disappear when precise redox potential and
kinetic data under identical conditions for all the complexes become available, but
the points for the ferrozine and the hexadentate Schiff base complexes lie well
away from the bipyridyl-phenanthroline trend. That the nature of the ligand
should have such a marked effect is surprising, particularly as peroxodisulphate
oxidation of Ru(bipy)32+and of Os(bipy)3'+ can be accommodated on the same
plot as Fe(bipy)3*+ and related compounds [31].
142 GARDNER, MEKHAIL, AND BURGESS

Acknowledgements
The authors gratefully acknowledge the award of a grant from the Royal
Society for the purchase of the spectrophotometer, and thank J. A. Brivati for con-
structing the thermostatted syringe-mixer unit used for the more rapid runs.

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Received June 12, 1973

Revised October 9, 1973