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ABSTRACT
There are few systems in which it has been possible to compare the substitution rates of
Ni(II), Pd(II), and Pt(II) square-planar complexes. This is largely due to the tendency of
nickel (II) to form octahedral complexes. However, the use of bidentate ligands having sul
phur donor atoms enables such a study to be carried out.
Rate constants for substitution reactions of square-planar complexes of Ni(II), Pd(II),
and Pt(II) containing bidentate sulphur ligands have been measured inwater and methanol.
Unidentate and bidentate nucleophiles have been used. A general mechanism is proposed to
account for the kinetic data.
The order of reactivity of square-planar complexes of Ni(II), Pd(lI) and Pt(II) is usually
given as:
Ni : Pd : Pt :1: 106 : : 1.
In the present investigation the order is Ni $, Pd, Pt. Changing the solvent from water to
methanol causes a -decrease in the rate constants but themagnitude of the decrease is depen
dent on the system being studied. The kinetic results are interpreted in terms of solvent and
bonding effects.
There have been many kinetic investigations of the rates and mechanisms of substitution
reactions of square planar complexes of the nickel triad (Basolo and Pearson 1962, Langford
and Gray 1965, Belluco et al. 1966, Peloso 1973, Cattalini 1970), Platinum (II) and Palladium
(II) substrates have been studied extensively but the amount of information available on the
substitution reactions of square planar Nickel (II) complexes is very limited. Square planar
Ni(II) complexes are less abundant than the corresponding Pt(II) and Pd(II) complexes
because of the greater tendency of Ni(II) towards octahedral coordination (Gray and
Ballhausen 1963). The square planar geometry of Ni(II) can be stabilised using strongly it
bonding ligands. In recent years a large number of planar Ni(II) complexes have been
prepared using ligands which contain sulphur donor atoms and delocalised ic-electron
systems. (McCleverty 1968, Coucouvanis 1970, Coucouvanis and Fackler 1966, Coucouvanis
and Fackler 1967). Platinum (II) and Palladium (II) will also form square planar complexes
with these sulphur ligands. These complexes have been the subject of recent kinetic
investigations (Pearson and Sweigart 1970, Hynes and Moran 1973, Pearson and Hynes
1971).
Experimental
The ligatids and complexes used were all prepared as described in the literature (Coucouvanis and
Fackler i966, Freund 1919, Pearson and Sweigart 1970). The complexes were prepared as either the
potassium or tetramethylammonium salts in order to confer maximum solubility in both water and
methanol. Reagent grade methanol was purified by refluxing with magnesium and iodine prior to use.
The sodium cyanide solutions were standardised by titration with silver nitrate. Ethylenediamine was
purified by distillation.
The rate constants were measured using either an applied Photophysics Stopped Flow device or a
Beckmann DB-GT u.v.-visible spectrophotometer equipped with a chart recorder. The Stopped Flow
data were recorded using a Tektronix model 51oo storage oscilloscope and a Polaroid camera. The
reactions were all run under pseudo-first-order conditions with the nucleophile present in excess at
25?C. The temperature was maintained constant towithin o.,1 . Sodium perchlorate was used as an
inert electrolyte tomaintain a constant o.1 mol drrf-3 ionic strength. Generally the psuedo-tirst-order
rate constants were obtained from plots of -in (AM&aoOiversustime. In the case of successive reactions the
rate constant of the faster step was determined at an isosbestic point of the slower step.When this was
not possible the Guggenheim method was used to calculate the rate constant of the fast step. Standard
errors were calculated as described in the literature (Swinbourne 1971).
The reaction products were identified by their u.v.-visible spectra.
2,-_
[s si
l C = tt CN
S R
FIG. 1
(1)
5.0 28.66
Solvent= H2 0
(2)
[Pd(ned)2]2- en 1o2[en],mol dm-3 lo4kobs,s
0.49 1.6
0.99 2.1
1.47 3.2
1.96 4.2
2.44 5.6
Solvent H 0
(3)
[Ptdned)2 ]2- en 10i ten], mol dm-3 10 kobS
0.99 2.5
1.98 4.25
2.96 6.45
3.92 7.45
4.88 9.4
Solvent= H 20
(4)
[Pd(cdc)2]2 - en 1
1io [en], mol dm-3 0
0.45 2.15
0.89 2.75
1.33 4.02
1.76 4.66
2.19 6.25
Solvent=H2 0
0.5 6.66
1.0 13.86
1.5 20.00
2.0 24.50
2.5 29.33
Solvent =H2 0
(6)
[Pt(ned)(GN)2]2 GNU Io02[CNT1hmol dm 3 kohs-i
0.5 3.66
1.0 8.75
1.5 12.25
2.0 14.5
2.5 19.75
Solvent =H2 0
(7)
K (ned) en ioU4en], mol dm'3 Io02kohs' s'i
4.00 1 2.67
6.oo 19.50
7.50 23.80
50.00 100.00
Solvent=H2 0
(8)
[Ni (ned)2] GN- 3
io31[CN1, mol dm k0h5,
0.75 0.36
1.75 2.36
2.50 4.91
5.00 20.50
10.00 -69.28
Solvent = Methanol
(g)
[Ni(ned)(CN)2 CN- Io2[CNlrnmoldm-3 kob"s
0.25 0.09
0.50 0.39
1.00 1.77
1.25 2.94
5.00 56.oo
Solvent Methanol
(1 o)
0.47 0.23
0.95 o.62
1.41 1.34
i.88 2.00
2.34 3.00
6.42 10.05
Solvent= Methanol
1.94 1.68
3.84 3.65
5.76 8.6o
7.64 12.30
9.51 17.23
Solvent = Methanol
(1i)
1.94 o.26
3.84 0.46
5 76 o.6o
7.64 o.go
9.51 1.04
Solvent= Methanol
0.5 3-97
1.0 8.oo
1.5 11.75
2.0 i8.17
2.5 22.25
Solvent= Methanol
(14)
K2(ned) en io2[en],moldm-3 102kobss
0.5 13.1
1.0 20.0
1.5 26.4
2.0 32.3
2.5 ~5-0
Solvent = Methanol
(15)
[Pd(ned)212 - en 1o2 [en], mol dm3 lo kobs, s
0.45 0.40
o.8g 0-75
1.10
1.33
1.76 1.40
2.19 i.65
Solvent = Methanol
('6)
[Pt(ned)2]2- en Io2[en], mol dm-3 10 kobs,s
0.45 0.50
0.89 0.70
1.33 o.85
1.76 1.05
2.19 1-45
Solvent = Methanol
(17)
-
[Ni(cdc)2 C- ioNG[CN, mol dm3 -kobs'S
4.92 1.01
9.84 2.93
19.70 8.92
29.50 19.20
39.40 32.50
Solvent = Methanol
(18)
[Ni(cdc) (CN)2]2 - CN- o [CN-, mol dm3 10okobSs
0.48 1.03
0.95 2.15
1.42 4-35
1.89 7-50
2.34 10.95
Solvent= Methanol
(19)
[Ni(cdc)2]2- en io2 [en], mol dm3 kobs s
0.25 1.37
0.50 3.28
1.00 7.86
1
1.50 13.6
2.00 19.00
Solvent = Methanol
(20)
[Pd(cdc)2 ]2 - CN- o2 [CN-, mol dm"3 1o0kobs5s'
1.98 5.10
3.29 6.92
4.28 7.75
4-94 8.6g
6.59 9.95
Solvent = Methanol
3.00 6.5o
4.12 7.1
4.75 7.6
(22)
[Pt(cdc) 212 102 [CN], mol dm3
-CN- 10 kobs
1.98 1.45
3.29 2.32
4.28 3-25
TABLE 2A
Solvent =Methanol
Substrate Nucleophile Rate const., s'
Solvent= H 0
- en x io0 [en]
[Ni(ned)212 (5.74 to.s)
[Pd(ned)2P- en (2.2 + o.) x Io- 2 [en]
[Pt(ned)2]2 en (1.96+oog) xi o-2 [en]
[Ni(ned)212 CN- v.fast
[Ni(ned) (CN)2]2 CN- v. fast
[Pd(ned) 2 2 - CN- 9.36 x 106 [CNA12 (a)
1 + 1.33 x 1o3 GCN-i
Figure i shows the structures of the complexes and ligands used in this study. The
pseudo-first-order rate constants for the reactions studied are shown inTables (1-22).The
second order rate constants and literature data are tabulated in Tables 2A and 2B. The nickel
complex of ned decomposes slowly inwater and methanol but it is appreciably more stable in
methanol than in water. Solutions of this compound were prepared and used within a period
of time that ensured negligible decomposition. It was found that both aqueous and
methanolic solutions of K2 ned react directly with ethylenediamine. The C, H, N, analysis of
this compound was the same (within experimental error) as that of K2ned.
Product C- 11.00, H-0.56, N -6.4
Calcd. for K2ned C- 11.26, H -o.47, N -6.5 J
The proton NMR spectra of the two compounds were identical. The product was not charac
terised further.
Fast
M(S - S) (en)? + en Fs M
M(en) )++S-S
+S-S
( M V) ( /5/\
..S
a- S N S S N
S-S +
k (NIA
t \M < _ . M
(0)
SCHEME 1
k' K [LI
kos
i + K [LI
where k'= kk3k5
k (k +k) + k ks
There is an additional solvent path for the reactions of [Pd(ned)212 and [Pt(ned)212 - in
methanol andIPd(cdc)2W2- in water. (vide infra).
IfK[LI < 1, then kobs-k' KLLJ. . . .Eqn. 1.
A plot of kob5 versus [LI yields a straight line with a slope of k'K. The intercept is equal to the
rate constant for the solvent path.
(. ./ \ slv- (/\5(S/\-S
LA) ) (C)
K2 +/I(
S N S S-S
S N k S/\5
(D)
SCHEME 2
Assuming the steady-state approximation for (C) and (D), for excess cyanide ion, the follow
ing relationship is obtained:
kk5 K K [LI2
obs ~ (i + KI [LI) (k2+ K2k5 [L])
where k" = 1
k2
It is apparent from Equation 2 that depending on the relative magnitudes of the various rate
and equilibrium constants, kobs may show first (K1 [LI > 0, intermediate first and second
or second order (K, [LI < i) dependence on cyanide concentrations. The differences in the
kobSdependence on nucleophile concentration for bidentate and unidentate nucleophiles is
fortunate because it provides ameans of testing the proposed mechanisms. The reactions in
volving ethylenediamine as the nucleophile are all firstorder in entering group. This agrees
with Equation i. The order of the reactions when cyanide is used as the nucleophile varied
from first to intermediate to second order as demanded by Equation 2.
TABLE 2C
Table aC shows the relative reactivities of Ni(II), Pd(II) and Pt(II) square planar
complexes for a variety of ligands and nucleophiles. Some literature results are included, for
comparison purposes. The general order of reactivity for square planar complexes of the
Ni(II) triad (Basolo i965, Peloso 1973, Reinhardt and Sparkes 1967) is given as:
Ni : Pd : Pt : o: 1-I7== : 1.
It is apparent that this order no longer holds for reactions involving the dithiolene ligands. In
complexes involving "normal" ligands (e.g. non it - bonding or weakly it-bonding ligands
such as NH, C1F, en) the greater reactivity of Ni(II) and Pd(II) relative to Pt(II) has been at
tributed to tte greater tendancy of the former to form five-coordinate species. The five coor
dinate species must be forrmed prior to substitution for all three metals according to the
generally accepted mechanism for square planar substitution reactions (Basolo and Pearson
1967). The mechanisms proposed in Schemes i and 2 postulate the formation of pentacoor
dinate species. The ability of a d8metal ion.to increases its coordination number from four to
TABLE aD
Solvent Effects
Table 2D shows the ratios of the rate constants for the reactions when measured inwater
and methanol. It was not possible for some reactions to validly compare the rate constants
due to changes in the order of the reactions on going from water tomethanol. In all cases the
rate constants are reduced inmethanol relative to water but there is considerable variation in
the magnitude of the decrease. However, there are a number of trends evident in the
experimental data. The ratio kH O/kMeoH is greater for cyanide ion than for
ethylenediamine. For uncharged nucleophiles the order of increasing suppression of rate is
Pt = Pd < Ni
Ni c Pt -< Pd.
The generally accepted factors affecting the reactivityof inorganic complexes in different
solventmedia are activitycoefficients, dielectric effects, solvation effects and dipole moment
effects (Glasstone Laidler and Eyring 1941). A review of the literature reveals that the amount
of work done on the comparison of the reactivities of inorganic complexes in different
solvents is very limited. The basic theory has been developed (Glasstone Laidler and Eyring
1941, Amis 1966, Frost and Pearson 1961) but very little quantitative data exists with which
the present results may be compared.-Most of the work carried out to date in this area has
been concerned with the effects of solvent on formation rate constants of inorganic
complexes (Pearson and Ellgen 1967, MacKellar and Rorabacher 1971, Bennetto and Caldin
197 1, Shu and Rorabacher 197 2) rather than substitution reactions (Blandamer and Burgess
1976, Belluco 1966).
On the basis of limited results presented itwould be purely speculative to try and attribute
the observed effects to any of the factors affecting reactions in solution. However, the results
provide a basis for further research in this area.
Conclusion
Despite the large amount of work on substitution reactions of square planar complexes in
the chemical literature, the fact that somuch of it is concerned with Pt(II) complexes appears
to be detrimental to the fuller understanding of the intimate factors affecting square planar
substitution generally. The results presented indicate some of the avenues for future research
in this area.
References
Amis, E. S. 1966 Solvent Effects on Reaction Rates and Mechanisms. New York. Academic Press.
Bas?lo, F. 1965 Substitution Reactions of Square Planar Adv. Chem Ser. 49
Complexes.
F. and Pearson, R. G. The Trans Effect inmetal
Bas?lo, 1962 Complexes. Prog, inorg. Chem. 4, 381.
Bas?lo, F. and Pearson, R. G. 1967 Mechanisms of Inorganic Reactions. 2nd edn. New York. Wiley.
Belluco, U. 1966 Displacements on some Pt(II) square in protic and dipolar
planar complexes
aprotic solvents. Coord. Chem. Rev. 1, 111.