The Rates and Mechanisms of Substitution of Square-Planar Complexes of Ni (II), Pd(II), AND

Pt(II) Containing Bidentate Sulphur Ligands in Water and Methanol

Author(s): M. J. Hynes and Patricia F. Brannick
Source: Proceedings of the Royal Irish Academy. Section B: Biological, Geological, and
Chemical Science, Vol. 77 (1977), pp. 479-493
Published by: Royal Irish Academy
Stable URL: http://www.jstor.org/stable/20494312 .
Accessed: 22/06/2014 06:48

Your use of the JSTOR archive indicates your acceptance of the Terms & Conditions of Use, available at .
http://www.jstor.org/page/info/about/policies/terms.jsp

.
JSTOR is a not-for-profit service that helps scholars, researchers, and students discover, use, and build upon a wide range of
content in a trusted digital archive. We use information technology and tools to increase productivity and facilitate new forms
of scholarship. For more information about JSTOR, please contact support@jstor.org.

Royal Irish Academy is collaborating with JSTOR to digitize, preserve and extend access to Proceedings of the
Royal Irish Academy. Section B: Biological, Geological, and Chemical Science.

http://www.jstor.org

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 [4791
40.

THE RATES AND MECHANISMS OF SUBSTITUTION OF SQUARE-PLANAR COM

PLEXES OF Ni (II), Pd(II), AND POOI)CONTAINING BIDENTATE SULPHUR LIGANDS
IN WATER AND METHANOL

By M. J. HYNES and PATRICIA F. BRANNICK

Chemistry Department, University College, Galway

(Communicated by D. A. Brown, M.R.I.A.)

[Received, 13 APRIL 1977. Read, 26 SEPTEMBER1977. Published, 30 DECEMBER 1977.1

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 dithiolene systems the order has been found to be approximately:

Ni : Pd : Pt:: :xo3 : 102 : 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).

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
480 Proceedings
ofthe Irish
Royal Academy
There have been very few kinetic investigationsof the substitution reactionsof isoligand
complexes of Ni(II), Pd(I1) and Pt(1I). In the systems examined differing ratios for the relative
reactivityof Ni(II), Pd(II) and Pt(II) complexes have been obtained. (Basolo 1965,Hynes and
Moran 1973). Consequently it has not been possible to examine in detail the factors affecting
the relative reactivitiesof complexes of thesemetals. In thiswork a number of isoligand
systems of Ni(II), Pd(II) and Pt(II) have been examined in terms of (a) the substitution
mechanism, (b) the relative reactivitiesof squareplanar complexes of the threemetals, and (c)
the solvent effects of the system. In some cases itwas not possible to study the complete series
due to the insolubilityor inertnessof the substrates.The substitution kinetics of complexes
which are soluble in both water and methanol were measured in both solvents. In previous
studies on substitution of Ni(II), Pd(II) and Pt(II) complexes, the reactions were carried out
in either water or methanol and therefore systems for which data are available in both sol
vents are rare. In this paper we report the kinetics and mechanisms of the substitution reac
tions of a series of square planar complexes of Ni(II), Pd(II) and Pt(II) with unidentate, and
bidentate nucleophiles inwater and methanol.

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

t M M = Ni(Il), Pd(ll), Pt(li)

l C = tt CN

S - S = C R = H, R N02 t-cyanodithiocarbir=ate (abrev. cdc).

S R

1, iiitroethylene-2,2 Dithiolate (abrev. ned)

FIG. 1

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 RoyalInstitute
ofChemistry Issue
Centenary 481
TABLE 1
(1 -22)

(1)

Substrate Nucleophile 104[en],mol dm3 kOb,,s

[Ni (ned)2]2- en o.5 3.00
1.0 3.96
1.5 5.00
2.0 7.93
2.5 12.00

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

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
482 ofthe
Proceedings Irish
Royal Academy
(5) -
[Pt(ned)2 ]2 CNo%1 CNJ, mol dm kobs' S

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

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 RoyalInstitute
ofChemistry
Centenary
Issue 483

(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)

[Pd(ned)212 CN 10o [CN1, mol dm-3 103kObs'

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

[Pt(ned)212 CN- io0 CNl, mot dmi3 103kb,s

1.94 1.68
3.84 3.65
5.76 8.6o
7.64 12.30
9.51 17.23
Solvent = Methanol

(1i)

lPt(ned)(CN)2]2 CN- io'lCN-l,moldm-I io3k bs

1.94 o.26
3.84 0.46
5 76 o.6o
7.64 o.go
9.51 1.04
Solvent= Methanol

PROC. R.I.A., VOL 77, SECT. B (MI

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
484 ofthe
Proceedings Irish
Royal Academy
(13)
[Ni (ned)2]2 - en lo [en], inol drnf3 kobs

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

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 RoyalInstitute
ofChemistry Issue
Centenary 485

(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

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
486 ofthe
Proceedings Irish
Royal Academy
(21)

[Pd(cdc) (CN)2 CN- 0o2 [CN1, mol dm 103kobs'S

3.00 6.5o
4.12 7.1

4.75 7.6

Solvent = Methanol 6.30 8.4

(22)
[Pt(cdc) 212 102 [CN], mol dm3
-CN- 10 kobs

1.98 1.45
3.29 2.32
4.28 3-25

Solvent= Methanol 4694 4.38

TABLE 2A

Solvent =Methanol
Substrate Nucleophile Rate const., s'

[Ni(ned)/2 en (914 +0.49)x IO[en]

-
[Pd(ned),]2 en 1.3x 10o3 + (7.1 + o.o6)x io-3 [en]

[Pt(ned) ]2- en 2 x 1o-3 + (5.46 + o.61) x lo-" [en]

[Ni(ned) 21 CN- (7.7 + 0.2) X 105 [CN]2
[Ni(ned) (CN)2 - ON (2.38 0.o1)X 104oICN

[Pd(ned) ,]2 2 CN - 935 7[CN]2

+ 374 [ON]l
I~~~~~~~~
103
[Pt(ned)2 - CN- 31.45 x [CN-P
1+692o [ON]
[Pt(ned) (CN)2]2 - CN- 6.o x1io3 + (1.04 + o.o6) [COW]
[Ni(cdc)2] CNO (2.00 + o.o3) x Io N]2

[Ni(cdc) (CN)2]2 CN- 2.67 x 1O3[CN]2

1 + 174 [ON]1
[Pd(cdc)2]2 - CN 3.2 x io-3 + 10.5 x 1o-2 [CN-]
[Pd(cdc) (CN)212 - CN- 4.75 x 10-5 + 6.o x 1o-4 [CN-]

[Pt(cdc),]2 - ON 0.429 [CN-]2

1+ 30.47 [ON]1
[Pt(cdc)(CN)2]2 CN- v. slow
[Ni(cdc)2]2 en (9.04 t O.3) x 102 [en]
K2(ned) en 6.x 10o2 +'ti2.8 +O.9)[n

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 RoyalInstitute
ofChemistry Issue
Centenary 487
TABLE 2B

Solvent= H 0

Substrate Nucleophile Rate const., s

- 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

9.46 x io5 [CNA]2 (a)

[Pd(ned) (CN) ]2 -CG
2 1 + 1.64x 10o2[CN
[Pt(ned)2]2- CN- (1.30 +o.o6 x 104G[CN]
[Pt(ned) (CN) V
]2 CN- (8.o + o. ) x io2 [CN-]
[Ni(cdc)22- CN- v. fast (b)
[Ni(cdc)(CN)2]2- CN- v.fast (b)
[Pd(cdc)2]2- CN- 920 [CN1] (a)
[Pd(cdc)(CN)2]2- CN- 66 [CN-1] (a)
1
[Pt(cdc)2 CN- 3.o05[CN (c)
[Pt(cdc)(CN)2]2 CN- 0.51 [CN-1 (c)
[Ni(cdc)2]2- en 4.7 x 1o0[en] (b)
[Pd(cdc)2]2 en 9 X1O- 3 + (2.38 + o.2o) x o- 2[en]
K2(ned) en (2.87 + o.o6 x 1o2[en)

(a) R. G. Pearson and M. J. Hynes 1971.

(b) R. G. Pearson and D. W. Sweigart 1970.
(c) M. J. Hynes and A. Moran 1973.

Results and Discussion

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.

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 488 ofthe
ProceedingsRoyal
Irish
Academy
Two reaction steps were observed when aqueous and methanolic solutions of [Ni(ned)2V2
reactedwith ethylenediamine.Rate constantswere obtained for both steps as the reactions
were sufficiently well separated. The rate constant for the slower step was the same (within ex
perimental error) as for the reaction of en with ned2- discussed above. The more rapid of the
two steps can therefore be confidently assigned to the substitution of ned in [Ni(ned)2P2 - by
ethylenediamine. This indicates that en reacts wit the liberated ned2- and not wit com
plexed ned2-. The Pd(II) and Pt(II) complexes of ned2- are stable in both aqueous and
metanolic solutions. The rate constants for the reaction of both [Pd(ned)2V2 and
-
[Pt(ned)2]2 with en are considerably less than the rate constant for the independent reaction
of ned2- with en. It is reasonable to assume that the observed reactions are the substitution of
the coordinated ned2- ligands by en. The liberated ned2- will react with en in a time scale that
is rapid compared to the measured reactions. In all the reactions studied, when the com
plexes containing two dithiolene ligands were reacted with cyanide ion as nucleophile, two
separate reaction steps were observed. As in previous work (Pearson and Sweigart 1970,
Hynes and Moran 1973, Pearson and Hynes 1971 the steps are assigned as follows:

M(S - S)2 + 2 CN - M(S - S) (CN)V + S - S2 Step 1

M(S -S) (CN)2 +2 2CN -- M(CN)2 Step 2
~~~~~~~~4
Only a single step was observed when ethylenediamine was the nucleophile. The reaction
sequence in the case of Ni(II) is
Slow
Ni (S- S)2- + en - S) + S - S2
Ni(S (en)0

Ni (S- S) (en)O+ 2en Fast. Ni (en)2+ + S - SI

For Pd(II) and Pt(II) the sequence is:

M(S - S)2- + en Slow > M(S - S) (en)? + S - S2

Fast
M(S - S) (en)? + en Fs M
M(en) )++S-S
+S-S

Mechanism for the substitution reactions with ethylenedtamine

(Chargeson complexes are omitted)

( M V) ( /5/\

(A) (B) (C)

..S
a- S N S S N
S-S +
k (NIA
t \M < _ . M

(0)

SCHEME 1

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 RoyalInstitute
ofChemistry Issue
Centenary 489
The subsequent steps are rapid for all three metals and will not affect the rate law. Assuming
the steady-state approximation for (C) and (D), for excess of cyanide, one obtains:

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.

Mechanism for the substitution reactions with cyanide ion as nucleophile

(Charges on complexes are omitted)
N
S S S jS S N

(. ./ \ 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])

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 490 Proceedings
ofthe Irish
Royal Academy
assumingk2 k k5K [LI,

kit KIC [LI'

abs 1 .... Eqn. 2.
1K1[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

Relative rates of substitution of Ni(II) Pd(II) Pt(II)

Dithiolate complexes in H 20 and MeO H

Substrate Solvent Nucleophile Ni: Pd: Pt

[M(ned)2, H2O en 3x106: 1 ::
[M(ned) ]2 HO0 CN- 1 :2
2~~~~~~~~
[M(ned) fCN3)] H,?O
CN- 5 :I
[M(cdc)21- H20 en 2X 106:1
[M(ned) ,I2- MeOH en 2 x 1o0: :1
IM(cdc) (CN)2P MeOH CN- ixio :I
Relative reactivity of Ni(II), Pd(II) and Pt(II) square-planar complexes

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

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 RoyalInstitutofChemistry Issue
Centenary 491.
five or six is usually attributed to the ability of the (n - 1)pz orbital of the metal (which is it
bonding in a square planar complex) to form a a bond with an incoming nucleophile (Gray
and Ballhausen 1963, Morgan and Tobe 1971, Zumdahl and Drago 1968). When this orbital
is involved in a delocal.sed it-electron system with the ligands, its ability to coordinate a fifth
or sixth group is reduced and consequently the square planar geometry is stabilised (Gray
1965, Shupack 1964, Gray 1964, Pearson and Sweigart 1970). It is apparent from Table 2C
that the relative reactivity of Ni(II) and Pt(II) square planar complexes appears to be insen
sitive to the i-bonding ability of either the ligands or nucleophile. However, the reactivity of
square planar Pd(Il) is very much reduced in complexes containing strongly i-bonding
ligands and the substitution rates become comparable to those of square planar Pt(II) com
plexes. This effect can be interpreted in terms of the availability of the (n - 1 metal orbital
)p,
for a-bonding. In Pt(II) complexes this orbital is relatively inaccessible irrespective of the
nature of the ligand system. In square planar Ni(II) complexes, even when the orbital is in
p,
volved in nt-bonding with the ligand system, it is still readily available for a-bond formation
with entering nucleophiles. This is verified by the normal substitution rates of Ni(II)
dithiolene complexes. However, the Ni(II) square planar complex with the extremely
strongly n-bonding maleonitrile dithiolate (mnt2) isan exception. The substitution ratesof
[Ni(mnt)2]P- with cyanide ion as nucleophile are very much reduced. This is obviously not a
thermodynamic effect since the mnt2l is displaced from [Ni(mnt)212 - even at low cyanide
concentration, albeit extremely slowly (Pearsonand Sweigart 1970).There are two extreme
cases possible for square planar palladium (II) complexes. The reactivity of complexes of
Pd(II)with non it-bondingor weakly i-bonding ligandsapproaches thatof Ni(II). Generally,
in this case the Pd(II) substitution rate constants are reduced by an order of magnitude
relative to Ni(II). On the other hand, when the ligands are strongly n-bonding (e.g. dithiolate
ligands), the rates become comparable to those of similar Pt(II) complexes. Therefore it
appears that the availability of the 5 pz orbital in Pd(II) complexes is sensitive to the ligand
environment. It is probably fortuitous that the general theory of square planar substitution
reactions is largely based on the reactions of Pt(II) rather than Pd(II) (Basolo and Pearson
1967, Benson 1968).

TABLE aD

Solvent Effects

Substrate Nucleophile kH O/MeoH

[Ni(ned)2I en 6
[Pd(ned)2 - en 3
[Pt(ned)2]2- en 3
[Pt(ned)212 CN- 286
fPt(ned)(CN)2]2- CN- 769
[Pd(cdc)2V- CN- 8761
[Pd(cdc)(CN)21 - CNU 110,000
[Pt(cdc)t]2 CN- 233
[Ni(cdc)2] en 52

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
492 Proceedings
ofthe Irish
Royal Academy
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

For charged nucleophiles the order is

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.

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions
 ofChemistry
RoyalInstitute Issue
Centenary 493
Belluco, U., Ettorre, R., Bas?lo, F., Pearson, R. G. and Turco, A. 1966 Activation Parameters
for some substitution reactions of acidodiethylenetriamineplatinum (II) complexes. Inorg.
Chem. 5, 591.
Bennetto, H. P. and Caldin, E. F. 1971 Solvent Effects on the kinetics of the reactions of Ni(II) and
Co(II) ions with and 2,2',2"-Terpyridyl./. chem Soc. (A), 2191.
2,2-bipyridyl
Benson, D. 1968 Mechanisms of Inorganic Reactions in Solution. London. McGraw-Hill. Chapter
2.
Blandamer, M. and Burgess, 1976 Kinetics and Equilibrium properties of Pentacyano (3,5
J. J.
dimethylpyridine)-Fe(II) and related anions in mixed aqueous solutions. J. chem. Soc. Dalton
1293.
L.
Cattalini, 1970 Replacements on d8 square planar complexes. Prog, inorg. Chem. 13, 263.
Coucouvanis, D. 1970 Dithioacid and 1,1-dithiolate Prog, Chem. 11, 233.
complexes. inorg.
D. of the 1,1
Coucouvanis, and Fackler, Jr., J. P. 1966 Sulfur Chelates III. Metal complexes
Dithiolato Anions S CC(CN)2". J. Am. chem. Soc. 88, 3913.
S2CS2", SaCNCN2~,
D. and Fackler, to Dithiolato
Coucouvanis, Jr., J. P. 1967 Sulfur Chelates IV. Sulfur addition
Complexes of Ni(II). J. Am. chem. Soc. 89, 1346.
Freund, E. 1919 ?ber die von Schwefelkohlenstoff auf Nitromethan. Chem. Ber. 52,
einiwirkung
542.
Frost , A. and Pearson, R. G. 1961 Kinetics and Mechanisms. 2nd edn. New York. Wiley, Chap. 7.
Gray, H. B. 1964 The Electronic Structures of Square Planar Metal ll.Inorg. Chem. 3,
Complexes
663.
Gray, H. B. 1965 Electronic Structures of Square Planar Metal Complexes. Transit. Metal Chem, 1,
240.
Gray, H. B. and Ballhausen, C. J. 1963 A Molecular Orbital Theory for Square Planar Metal

Complexes./. Am. chem. Soc. 85, 260.

Glasstone, S., Laidler, and Eyring, H. 1941 The Theory of Rate Processes. London. McGraw
K.J.
Hill, Chap. 8.
Hynes, M. and Moran, A. 1973 Rates and Mechanisms of Substitution reactions of Platinum
J.
dithiolato-complexes. J. Chem. Soc. Dalton 2280.
Langford, C. H. and Gray, H. B. 1965 Ligand Substitution Processes. New York. Benjamin, Inc.,
Chapter 2.
McCleverty, A. 1968 Metal 1,2-Dithiolene and related Complexes. Prog, inorg. Chem. 10, 49.
J.
MacKellar, W. J. and Rorabacher, D. B. 1971 Solvent Effects in Coordination Kinetics./. Am.
chem. Soc. 93, 4379.
Morgan, T. D. B. and Tobe, M. L. 1971 Substitution Reactions of five coordinate Complexes I.

Inorg. Chem. Acta 5, 563.

Pearson, R. G. and Ellgen, P. 1967 Rates and Mechanisms of formation of some Ni(II) complexes
in methanol. Inorg. Chem. 6, 1379.
Pearson, R. G. and Hynes, M. J. 1971 The Rates and Mechanisms of Substitution Reactions of
Palladium (II) Dithiolate Complexes./. Coord. Chem. 1, 245.
Pearson, R. G. and Sweigart, D. W. 1970 The Rates of Substitution and Mechanisms
Reactions of

Square Planar Ni(II) Dithiolate Complexes. Inorg. Chem. 9, 1167.

Peloso, A. 1973 Kinetics of Nickel, Palladium and Platinum Complexes. Coord. Chem. Rev. 10, 123.
Reinhardt, R. and Sparkes, R. 1967 Kinetics of the Consecutive Substitutions of ammonia by
chloride ion in tetraammine palladium (II) ion. Inorg. Chem. 6, 2190.
Shu, F. R. and Rorabacher, D. B. 1972 Solvent Effects in coordination kinetics. Inorg. Chem. 11,
H95
Shupack, S. I. 1964 of the maleonitriledithiolate
Spectral Properties complexes of nickel, palladium
and platinum./. Am.
86, 4594. chem. Soc.
Swinbourne, E. S. 1971
Analysis of Kinetic Data. London. Nelson.
Zumdahl, S. S. and Drago, R. S. 1968 A molecular orbital study of the trans influence and kinetic
trans effect in square planar Pt(II) complexes./. Am. chem. Soc. 90, 6669.

This content downloaded from 62.122.79.78 on Sun, 22 Jun 2014 06:48:48 AM

All use subject to JSTOR Terms and Conditions