Dkajsçksda
Dkajsçksda
Dkajsçksda
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
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.
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
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
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
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
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
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
+1
+10
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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