Polyhedron Vol. 5, No. 12, pp. 2113~2115,1986 0211-5387/86 s3.00+.

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Printed in Great Britain 0 1986 Pergamon Journals Ltd.

COMMUNICATION

VARIATION OF ACTIVATION VOLUMES FOR AQUATION OF

CHLOROAMINECOBALT(III) COMPLEXES
GEOFFREY A. LAWRANCE

Department of Chemistry, The University of Newcastle, New South Wales 2308, Australia

(Receiued 6 June 1986; accepted 23 June 1986)

Abstract-Activation volumes for aquation of cis-[Co(en),(NO,)Cl]+, trans-[Co(en),

CWlI +, cis-a- and cis-#?-[Co(trien)Cl,]+ have been determined, and are compared with
values reported for a range of chloroaminecobalt(II1) complexes. Variation of reported
AV* in terms of, particularly, solvation effects is discussed.

The mechanistic value of measured activation vol-
ume (Al’&,) in reactions of coordination complexes
has been the basis for extensive study.ld At least
for reactions involving exchanges of small neutral
molecules, interpretation of AV&, in terms of
volume changes arising from displacement of par-
ticles at the active site seems relatively straight-
forward.6 This is because motions of small neutral
molecules should not involve any large changes in
solvation from precursor to transition state. If
we assign to the experimental activation volume
separate contributions from intrinsic displacement
(Al’&) and solvation (A&$,,) terms, where the
former term carries the mechanistically significant
information, it becomes clear that interpretation of
AI/&, values depends on small AI/$, components
or at least an understanding of the significance of
this term in various circumstances.
With ionic leaving groups, a dissociative tran-
sition state may involve formation of, or substantial
motion towards formation of, a new charge centre.
In polar solvents, significant electrostriction of the
new charge centre with concomitant changes in
molar volumes of participating solvent molecules
will occur. The result is seen experimentally as a
negative contribution to AV& Variation in
AV,Z,, from + 1.2 to -9.9 to - 18.5 cm3 mol-’ for
[Co(NH,),L-J”+ hydrolysis’** as L varies from OH,
to Cl- to SO:- can be used to illustrate the role
of electrostriction. While these complexes aquate
by essentially the same mechanism, clearly AV&,
alone is not mechanistically definitive, being
masked by solvent electrostriction terms in the
latter two examples. , 3.16 + 0.07(345),
2113
The significance of the problem can be gauged
further by the observation that AV& for chloride
aquation from a range of cobalt(II1) amines vary
between - 10 and + 11 cm3 mo1-‘.8*‘3 Here,
differences must lie not just with the central metal
ion or leaving group but also with the non-leaving
groups and overall charge. We have been working
to extend the number of such examples for which
AK& have been measured. Recently, AV,f,, for
aquation of [Co(NH,),Cl]‘+, trans-[Co(NH,),
(NH,CH,)Cl]‘+ and [CO(NH,CH,),C~]~+ were
compared. ’ 3 It was found that A V& becomes more
positive with increasing molar volume of the cation.
Here, we report AV&, for several other chloro-
aminecobalt(II1) complexes, and examine the over-
all trend.
With stereochemically unconfined cobalt(II1)
complexes, isomerization can accompany spon-
taneous aquation,14 which can make interpretation
of AI/&, more difficult. The complexes cis-[Co(en),
(Nwc11+, trans-[Co(en),(CN)Cl] + and cis-
[Co(trien)Cl,] + were chosen for study because they
are reported to undergo aquation with retention of
configuration.‘-’ Hydrolyses were followed in 0.1 M
HClO, on a Varian 635 spectrophotometer fitted
with a high-pressure cell at a fixed wavelength and
a constant temperature. Minor enhancement of
observed rate constants with increased pressure
were observed in all cases. Results { 104k,,b, (s- ‘)
[P(bar)]) obtained were as follows: cis-
[Co(en),(NO,)Cl] + : 3.63 + 0.10(l), 3.78 + 0.20
(345), 3.92 + 0.15 (690), 4.03 f 0.10(1035), 4.23 + 0.05
(1380); trans-[Co(en),(CN)Cl]+: cis-a-3.10 & 0.09(l),
3.20 k 0.10(690), 3.36 f 0.16
2114 Communication

(1035), 3.45 &- O.lO(1380); cis-cr-[Co(trien)C1,]+:1.89 transition state for aquation reactions in complexes
f 0.06(l), 2.01 + 0.13(345), cis-/I-E2.19 + 0.11(690), where chelate rings exist may differ from the situ-
2.33 + 0.06(1035), 2.50 + O.lO(1380). Further, ation with simple ammines if molecular relaxation
aquation of cis-jI-[Co(trien)Cl,] + was reexam- and rearrangement to permit a choice of geometry
ined, since deviation from first-order behaviour in the successor are involved in part in the activation
was more substantial than expected in the initial process for aquation.
study,” limiting accuracy of determined kobs. Except for [Co(tren)Cl,] ’ and [Co(dtcd)
The revised results, using a different sample of W,)Cll +, all complexes show a quite close
complex, which yields a different AV&,, are linear relationship between AI/Z, and AS&,. For
for cis+[Co(trien)Cl,] +: 14.7 * 0.4(l), 15.0 f0.3 the [Co(tren)Cl,]+ ion, the first hydrolysis is a
(345), 15.5 f 0.4(690), 16.1 f 0.4(1035), 16.4 f 0.3 composite reaction since two non-equivalent sites
(1380). Experiments were conducted at 35, 35, 27 exist, one of which may be especially labile;”
and 25”C, respectively. Activation volumes for com- observed Al/.& in this case may be less accessible
plexes were calculated in the usual manner,5 and to interpretation. Alone amongst the complexes,
are included in Table 1, along with activation aquation of [Co(dtcd)(N,)Cl]+ involves loss from
enthalpy and entropy values previously deter- a large substituted and unsaturated macrocyclic
mined, and data for similar complexes. complex, which may represent a special situation.”
Although in all cases chloride aquation from Since intrinsic and electrostrictive effects should
cobalt(II1) is occurring, with the consequent expec- usually contribute in a like sense to AI/&, and
tation of a basic mechanistic constancy, it is clear AS:,, a correlation between these terms is not
from data in Table 1 that both AI’& and AS& unexpected, and has been addressed previously.”
vary appreciably. Since a strictly limiting dissoci- One interpretation of the significantly positive
ative character is unlikely,14 variations could in A I’& for [Co(tren)Cl,] + and [Co(dtcd)(N,)Cl] +
part reflect differing Co 3+-C1- separation in the could be to assert a significant shift towards a
transition state, which would affect both AI’:,, and limiting dissociative mechanism in these cases.
AV;,, terms. In any case, the sensitivity to particu- However, there seems no special case for this
larly non-leaving groups is apparent. Variation in assertion at least with the trans-[Co(en),Cl,]+ ion,
the series trans-[Co(en),(X)Cl] + is notable, since where A V,&, is also large and positive;’ thus it may
AI/:, changes with trans-X group from + 11 cm3 not be an acceptable interpretation in general.
mol-’ (X = Cl-) to +0.7cm3 mol-’ (X = N;) to Reactions of cobalt(II1) complexes in acid, while
-2.0cm3 mol-’ (X = CN-). At least for the first believed to be dissociative in nature, have rarely
two, aquation occurs with some isomerization.‘4 been considered to involve a limiting mechanism.
Since isomerization reactions alone in cobalt(II1) Lifetimes of any intermediates are probably in no
chemistry can exhibit large positive AI’&” vari- more than the picosecond range, which should
ations observed may reflect the amount of not permit complete solvent reorganization in the
rearrangement in the transition-state formation. activation process itself. Varying the non-leaving
The extent of bond stretching necessary to reach the groups may vary the lifetime of the activated

Table 1. Activation parameters for aquation of chloroaminecobalt(II1) complexes

k25’c
AH+ AS’ AV+
Complex” (s-l) (kJmol-‘) (JK-‘mol-‘) (cm3 mol - ‘) Reference
[CO(NH,),CI]~ + 1.7 x 10-6 93 (& 1) -44 (f 3) -9.9 (k 0.5) 8
trans-[Co(NH,),(NH,CH,)Cl]‘+ 1.1 x 10-s 95 (* 2) -19 (+ 6) -4.6 (+ 0.5) 13
[CO(NH,CH,),CI]~ + 4.0 x 10-s 95 (+ 1.5) -lO(k4) -2.3 (+ 0.4) 13
cis-a-[Co(trien)Cl,] + 1.6 x 1O-4 90 (* 1.7) -24 (+ 6) - 5.0 ( + 0.4) *, 17
cis-/I-[Co(trien)Cl,)+ 1.5 x 10-3 88 (k 1.7) -11 (+ 6) - 2.0 (+ 0.6) *, 17
cis-[Co(tren)Cl,] + 3.0 x 10-3 74 (* 2) -45 (+ 6) +7.3(+ 0.4) 11
cis-[Co(en),(NO,)Cl] + 1.2 x 10-4 90 (&- 0.5) - 17 (&- 2) -2.9 (+ 0.3) *, 15
Pans-[Co(en),Cl,] + 3.1 x 10-s 115 (+ 5) +56 (+ 15) +11.0(+0.6) 9, 23
trans-[Co(en),(CN)Cl] + 7.8 x lo-’ 94 (+ 0.6) -9 (* 2) - 2.0 ( f 0.4) *, 16
trans-[Co(en),(N,)Cl] + 2.2 x 10-4 93 (+ 4) +2 (* 11) +0.7 (f 0.1) 12, 24
tmns-[Co(dtcd)(N,)Cl]+ 4.6 x 1O-4 77 (* 2) -51 (+ 6) +8.3 (+ 0.4) 10
“en = ethane-1,2-diamine, trien = 1,8-diamino-3,6_diazaoctane, tren = N,N’-bis(2-aminoethylkzthane-1,2-diamine,
and dtcd = 5,12-dimethyl-1,4,8,1 l-tetraazacyclotetradeca-4,11-diene.
*This work.
 Communication
groups may vary the lifetime of the activated
complex a little. In a timescale regime where solvent
reorganization may be occurring at a more
“leisurely” pace, the actual progress to, and
“resting” period in, the transition state for a particu-
lar molecule may markedly affect the AI/$,,, com-
ponent of A V& when displacement of ionic groups
is involved. An increase (in a positive sense) in
AI/&, as the size of the cation increases or the type
of ligands vary may then reflect a small change in
either the amount of bond extension in forming the
transition state or its lifetime, or both. No abrupt
change in mechanism need be considered.
Complexes with markedly positive AV& such
as [Co(en),Cl,] +, may involve more substantial
rearrangement in forming the transition state, with
electrostriction of new charge centres being offset
by displacement of electrostricted water molecules
into the bulk solvent by motions of the non-leaving
groups. There may be a prospect for examining this
concept. It is known, for example, that solvolysis
of [Co(NH,),(OCH. N(CH,),)]3’ in H,O or
OCH . N(CH,), yields essentially identical
AV&? perhaps indicative of small AV& contri-
butions to AI/&. However, isomerizations of
CCo@MWPH2)1z+ complexes, even from H,O
to D,O as solvent,” show differences in AV,2,,
which probably relate to variations in AI/$,. Vari-
ations in AV$, for trans-[Co(en),Cl,] + solvolysis
compared with those for trans-[Co(en),(CN)Cl]+,
for example, may probe the comparative roles of
AV$,,, terms in each case. It is clear that a greater
understanding of the part played by solvation terms
is important for a more detailed interpretation of
AV&, when ionic leaving groups are involved.
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