860 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY

[ CO{NH))s (N))r (CTU~~I~~~ilon) [CO{NH))sJ2+ +.N) ~Co(II)+ NH) + N2

(Redox decomposition).
In the following example, CT(LMCT) excitation causes the photoisomerization.
Isomerization
)[CO{NH))s (OND)r;
(Linkage isomer)

6.9.5 Photochemical Reactions of the Cr(llI) Complexes

For the Cr(III) complexes, analogous to those of the Co(lll) complexes, there is no redox reaction
under the comparable conditions. It is reasonable. For the Co(lll)-complexes, Co(ll) can be generated
as an intermediate, i.e. reduction of Co(Ill) to Co(ll) is feasible. On the other hand, for the Cr(lll)
complexes, it is unlikely to generate the Cr(ll) intermediate state. This can be rationalised in terms of
their E>-values, e.g. 1.8 V for [Co(aq)]3+/[Co(aq)]2+ and -0.42 V for [Cr(aq)]3+/[Cr(aq)]2+ couple, i.e.
reduction of Co(lll) to Co(ll) is thermodynamically easier. Other characteristic features of the
photochemical reactions of the Cr(lll) complexes are discussed below.
The quantum yield increases w"ith the increase of temperature. It indicates the requirement of a
thermal activation energy. It is suggested that after the primary photochemical process, it requires the
thermal activation energy for the subsequent reactions. Consequently, the overall process is slow. Here
it may be mentioned that for the analogous Co(III)-complexes, there is no need of such thermal
activation energy. Because, for the Co(III)-complexes, after the primary photochemical process, a very

Differences in photochemical reactions of the analogous

Co(lIl) and Cr(llI) complexes
• For the Co(III)-complexes, there may be both substitution and redox reactions depending on
the conditions, but for the Cr(lll) complexes, redox reaction does not occur.
• For the Co(lll) complexes, photoexcitation can generate a reactive intermediate Co(II) (which
is labile and reducing) while for the Cr(III)-complexes no such reactive intermediate like Cr(ll)
is generated. In fact, photoexcitation of the Cr(lll) complexes, probably gives a long-lived 2Eg
state that subsequently participates in the reactions requiring a the thermal activation energy.
• For the Co(lll) complexes, after the primary photoexcitation, there is no need of thermal
activation energy for the subsequent reactions. The Cr(III) complexes need a thermal activa-
tion energy for the subsequent reactions.
• Reactions of the Cr(Ill) complexes are slower.
• For the Cr(Ill) complexes, quantum yield is more or less insensitive to the wavelength in the
range 300-700 nm. For the Co(lll) complexes, light of 370 nm favours the CT excitation for
the redox process while light of 550 nm leads to ligand field excitation to favour the substitu-
tion reaction.
• For the Cr(III)-complexes, two possible reactive intermediates, i.e. 2Eg and 4T2g are suggested.
The 2Eg state (low-spin ~g) having a vacant orbital in the t2g -level experiences an associative
activation while the 4T2g state (~g e~) having an enhanced electron density in the antibonding
orbital experiences the dissociative activation in the subtitution process. LF excitation in the
Co(lll) complexes favours the dissociative activation due to the weakening of metal ligand
bond.
REACTION MECHANISM: ELECTRON TRANSFER REACTIONS AND PHOTOCHEMICAL REACTIONS OF METAL COMPLEXES 861

reactive centre which is Co(ll) is generated. In the case of Cr(lll) complexes, there is no such possibility
of generation of Cr(ll) species. In fact, even after the photoexcitation, Cr(lll)-state (an inert centre) is
still maintained. It is suggested that photoexcitation of the Cr(lll) complexes produces a relatively
long-lived doublet state 2Eg which subsequently participates in the substitution reactions. This
long-lived 2Eg state requires the thermal activation energy for its subsequent substitution reactions.
(A) High activation energy (ca. 60 kJ mol-I) and effect of temperature: The quantum yield (<I»
is almost insensitive to the wavelength of irradiation in the range 300-700 nm but the quantum yield
increases with the rise of temperature. In fact, this high activation energy (ca. 60 kJ mol-I) is unusual
for a photochemical reaction. This can be explained by considering the requirement of a thermal
activation after the photoexcitation. This step of thermal activation is only possible, if the photochemically
produced intermediate is sufficiently long-lived (life-time ~ 1 ms). Thus to explain the effect of tem-
perature on <1>, we must consider an intermediate (produced photochemically) that will survive at least
1 ms. The probable intermediate 2Eg and/or 4T2g (to be discussed later) is still Cr(lll) (d3) which is inert
and it needs a thermal activation for substitution or racemisation.

Table 6.9.5.1 Photochemical reactions of the Cr(lll) complexes (cf. A. W. Adamson et ai, J. Am. Chem. Soc.,
80,3865, 1958; R. A. Plane et ai, ibid, 79, 3343, 1957; Inorg. Chern., 3,231, 1964).

Complex/System Wavelength of Reaction Quantum Yield

irradiation A (nm) product ep (mol einstein-I)

[Cr(NH 3)6]3+ 320-600 [Cr(NH 3h(OH 2)]3+ 0.32

[Cr(NH 3h(OH 2)]3+ 320-600 [Cr(NH3)4(OH 2h]3+ 0.25
[Cr(NH 3)iOH 2h]3+ 320-700 [Cr(NH 3)3(OH 2)3]3+ 0.16
[Cr(NH 3)3(OH 2)3]3+ 320-700 [Cr(NH 3h(OH 2)4P+ 0.014
[Cr(NH 3)iOH 2)4]3+ 320-700 [Cr(NH 3)(OU2h]3+ 0.0018
[Cr(NH 3h(NCS)P+ 560 [Cr(NH 3h(OH 2)]s+ 0.013
[Cr(OH 2)6]3+ + Ct 370 [CrCl(OH2h]2+ 0.006
[Cr(OH 2)o]3+ + NCS- 400 [CrNCS(OH2)s ]2+ 0.0024
(+)[Cr(C 20 4hP- 370 Racemization 0.045
(no decomposition)

(B) Nature of the intermediate state produced through the primary photoexcitation process in
the case of Cr(III) complexes: To understand this aspect, it is required to consider the energy level
diagrams of the Cr(lll) complex (Fig. 6.9.5.1).
The spin allowed transitions in the Cr(lll) complexes are:
4
A2g
(F)~ 4 T2g (F), 4 A2g (F)~ 4 T1g (F), 4 A2g (F)~ 4 T1g (p).

The third transition (i.e. \)3) very often merges with the strong charge transfer band. The spin forbidden
transition is:
4A
2g
(F)~ 2 Eg (F)

2Eg state arises from the low spin configuration of t2~' i. e. (i J, )(1')( ) where one level is remaining
vacant.
(a) Doublet state, i.e. 2Eg as the reactive intermediate: It is suggested that the excited quartet states
[i.e. 4Tlg (P), 4T1g (F) and 4T2g(F)] will rapidly revert to the ground state but in this deexcitation process,
862 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY

Internal
conversion

(Arising from 4 F)

ISC
(Intersystem
crossing, -----.2 Eg (t~g, low spin)
radiationless (Arising from 2G).
transition)

~A -,
_---.;~
, -=:a..___ _ 4
A2g
(~g , high spin)

(Arising from 4 F)

Fig. 6.9.5.1 Energy level diagram of the octahedral complexes of Cr(lll) and transition in terms of Jablonski diagram.
2Eg state actually represents two states 2ER and 2T1R arising from 2G, i.e. 2T1iG), 2EiG) = 2EiG) (cf. Fig. 7.14.5.6).

population density of the doublet state (i.e. 2Eg ) will increase to some extent and this doublet state is
relatively long-lived because the transition from the 2Eg state to the ground 4A 2g state is spin forbidden.
This is why, some workers believe that 2Eg is the intermediate generated from the photoexcitation
process.
The 2Eg excited state (low spin t1g ) generates a vacant orbital at the t2g level. Availability of this
vacancy at the 12g level favours the associative activation in the photosubstitution process. It may be
noted that in the thermal substitution reactions, Cr(lll) also adopts the associative path with a high
activation energy.
The quantum yield ((jJ) is not sensitive to the wavelength of irradiaion in the region 300-700 nm. It
indicates that the reactive intermediate is the lowest excited state which is not produced directly
through the photochemical excitation. It supports the 2E g state as the reactive intermediate. Thus, if
the 2Eg state is considered to be responsible as the reactive intermediate then the photochemical yield
should depend on the life period of this doublet state. It has been noted that the quantum yieldfor the
photoaquation of [Cr(NH3)x(OH2)6 _ x]3+ decreases gradually from [Cr(NH3)6]3+ to [Cr(OH2)6]3+.
This observation can be explained by considering the energy difference between the states 2Eg and 4T2g •
This energy difference is maximum for [Cr(NH 3)6]3+ while it is minimum (ca. 30 kJ mol-I) for
[Cr(OH 2)6]3+ (cf. NH3 is stronger field ligand than H20). In the case of [Cr(OH2)6]3+, by using the
thermal energy, population density of the 2Eg state may decrease due to the promotion to the 4T2g
state and thence to the 4A 2g state (ground state).
2E
g
thermally
)
4
T2g (allowed)
)
4
A 2g (ground st ate )
This indirect path (described as the leakage path) reduces the life-time or population density of the
2Eg state which is supposed to be the reactive intermediate. This indirect path to reduce the life time of
REACTION MECHANISM: ELECTRON TRANSFER REACTIONS AND PHOTOCHEMICAL REACTIONS OF METAL COMPLEXES 863

2Eg state is most efficient for the [Cr(OH 2)6]3+ complex in the series [Cr(NH 3)x(OH2)6_x]3+. The efficiency
ofthis leakage mechanism increases with the decrease ofx in the series. It explains the increasing trend
of quantum yield for the photoaquation of [Cr(NH3)x(OH 2)6-x]3+ with the increase of x.
(b) Quartet state as the reactive intermediate: Some workers believe that 4T2g state, i.e. quartet
i.
state is the reactive intermediate having the electronic configuration t2; e This state experiences the
Jahn-Teller distortion. Because of this J.T. distortion, the geometry of the excited quartet state is
different from that of the nondistorted ground state. Because of this difference in symmetry between the
distorted excited state and nondistorted ground state, the life-time ofthe excited quarlet state increases.
Because of the J.T. distortion, the excited quartet state is also labile.
In the 4T2g state (t~g e~), accumulation of electron density in the antibonding orbital weakens the
metal-ligand bond. This favours the dissociative activation in photosubstitution. The J.T. distortion
also favours the dissociative activation. Here it is worth mentioning that the 2Eg state and 4A 2g ground
state (i.e. thermal reaction) favour the associative activation.

Nature of the reactive intermediate: 2Eg VS. 4T2g (F)

• Enhanced life-time of the 2Eg-state arises due to the spin-forbidden transition to the 4A 2g
ground state. However, its life time may decrease through the indirect leakage path.
• Enhanced life time of the 4T2g -state arises due to the symmetry forbidden transition to the
ground state which is nondistorted while the excited 4T2g state is distorted (J.T. distortion).
• In the photosubstitution process, the 2Eg state (low spin ~g) favours the associative activation
while the 4T2g state (~ge~) favours the dissociative activation. In the thermal reaction, the
ground state adopts the associative path with a high activation energy.
• In fact, in the photochemical reactions of the Cr(lll) complexes, there are evidences for both the
2Eg (doublet state) and 4T2g (quartet state) states to represent the reactive intermediate.

(C) Adamson's rules: Adamson had formulated some empirical rules to explain the results of
photochemical reactions of [Cr(NH3)5X]2+ (X- = halide).
(i) In [Cr(NHJJsXf+, the ligands are at the ends ofthree mutually perpendicular axes. On irradiation,
the ligands will be labilized most along the axis having the lowest average ligand field strength.
(ii) If there are two different ligands along the labilized axis, the ligand having the higher ligand
field strength will be preferably labilized.
Thus for [Cr(NH3)5X]2+, the trans- ligands NH3 and X will be labilized most and between these two
ligands, NH 3 (having higher ligand field strength) will be preferably labilized.

[CrBr(NH 3 )sJ+ +H20~[ CrBr(NH 3 )4 (OH 2)J+ + NH 3

However, there are exceptions to these rule.
The ~ V* values for photoaquation of [Cr(NH3)5X]2+ and [Cr(NH 3)6]3+ are negative for aquation of
both NH 3 and X-. These data support the Id-mechanism where the dissociated fragments in the T.S.
put an enhanced electrorestriction over the solvent. This is reasonable as the excited state (4T2g )
accumulates more electron density in the antibonding eg* orbital from the nonbonding t2g -orbital and
this will weaken the metal-ligand bond to favour the dissociative activation. It may be noted that in the
thermal reactionsm, the Cr(III)-complexes adopt the associative activation.
(D) Interpretation of Adamson's Rule in photosubstitution reaction in terms of crystal field
theory (Ref. A.W. Adamson, Coord. Chem. Rev., 3, 169-188, 1968): The rules are applicable for both
the Co(III) (If, low-spin, i.e. t~g) and Cr(III) (d 3, i.e. ~g) complexes for which the ligand field transitions
864 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY

are quite similar (cf. Figs. 7.14.5.5, 7.15.2.4). But, for the Co(lll) complexes, the LF band and CT band
very often overlap and the Co(III)-complexes very often experience the photo-redox reactions because
of the ease of reduction of Co(lll) to CoCII). Here we shall illustrate the rule taking the Cr(III)-com-
plexes as the representative ones.
It is suggested that the quartet excited state (4T2g for ~ge~) of the Cr(III)-complexes is the reactive
intermediate for the photosubstitution process. The excited quartet state (t1ge~) experiences the Jahn-
Teller distortion generating the elongated two trans-L-M-L bonds (c.! z-out distortion). Because of
this significant difference in the geometries of the undistorted ground state (4A 2g , ~g) and excited state
(4T2g , t~g eg1), life time of the excited quartet state is ~ncreased as the transition, 4T2g -7 4A2g experiences
the Franck-Condon barrier. For the difference in the structures of 4A 2g and 4T2g states, the Franck-
Condon vertical transition (4A 2g ~ 4T2g ) produces the excited state (i.e. 4T2g state) at a higher vibrational
level (cf. Fig. 7.4.1.3).
In the unsymmetrical octahedral complexes, the average ligand field strength along the three mutu-
ally perpendicular axes will not be the same and the 4T1g and 4T2g states will split. This splitting pattern
for the cis-ltrans-[CrIII A 4X 2] complex is shown in Fig. 6.9.5.2. For the [CrIll A4X2 ] complex, orientations
of the ligands along the mutually perpendicular axes are as follows:
(i) cis-complex (two types of axes): A-A, A-X, A-X; Average ligand field strength: A-A axis
) A-X axis.
-----------
4T 1g (P)-------tl;,---
--- ---
.........
.........
...... --._-------

-----------
4T 1g -------<.<: .......
--- ---
............
Antibonding orbital projected
towards the stronger field axis
{

(t:ge:)~2g1 <=::~""~/~~Eo v:' liI

I
1{(::t:n:n~:::::prOjectedtowardS
the weakerfield axis
~ lil {3 (i.e. X~ - M- X
10Dqo VI (L 1 band) " " ~--r-_J--(L_':_b_an_d_)-r-'" axis for trans, X - M - A axis for cis)
I v; (L~ band) Lowest excited quartet state
(t2~) 4~g---";'._-'-- ---..I~___ (Longer wavelength
component of the L1 band)

.1E o determined by the average ligand field strength difference between the A-M-A and X-M-X axes (for the
trans-complex) and between the A-M-A and A-M-X axes (for the cis-eomplex) . .1Eo (trans): .1Eo (cis) 2:1. =
Fig. 6.9.5.2 Term diagram for the tP (e.g. Crill) octabedral (Oh) and less symmetric (D 4h , C2) complexes (cf Figs.
7.14.5.5, 7.15.2.1).
~ote: .Even fo~ the perfectly octahedral complexes like [CrIllL(), the 4T2g (i.e. (~.':e/) state experiences a distortion (J.T.
distortion) and In fact, this excited state is structurally different from the ground state eA2g, (2;). Thus, the vertical Franck-
condon transition, 4A 2.': ~ 4T2g produces the excited at a higher vibrational level. The excited state may thermally
equilibrate before emission to have the lower vibrational level at the excited state. Then emission (due to the return to the
4A 2g state) will occur to a higher vibrational level of the ground state «(1 Fig. 7.4.1.3).
REACTION MECHANISM: ELECTRON TRANSFER REACTIONS AND PHOTOCHEMICAL REACTIONS OF METAL COMPLEXES 865

(ii) trans-complex (two types of axes): A-A, A-A, X-X; Average ligand field strength: A-A
axis) X-X axis.
(cf positions of A (=NH 3, say) and X- (halide, pseudohalide, say) in the spectrochemical series; NH 3
is a stronger field ligand than X-).
The magnitude of splitting (/1£0) of the quartet state (4T2g ) depends on the difference in the average
ligand field strength between the two types of axes. The average ligand field strength difference between
the A-A and X-X axes in the trans-complex is twice the difference between the A-A and A-X
axes in the cis-complex. This is why, in the trans-complex, splitting of the quartet state is more.
Because of this splitting, the lowest ligand field band (say L}, v I = 4A 2g ~ 4T2g ) will undergo splitting
into two components, say Li(vi) and Li'(v~') where vi' ) vi. The vi transition (longer wavelength
component of the L} band) gives the lowest quartet excited state (in terms of the spin allowed ligand
field excitation) which accumulates the electron density in the antibonding orbital to weaken the metal-
ligand bond. The L~ band (i.e. v: transition) leads to the accumulation of electron density in the
antibonding orbital projected towards the weaker ligand field axes X-M-X (for the trans-
complex) and A-M-X (for the cis-complex). Less splitting of the 4T2g state corresponds to the
higher value of vi. Obviously, the higher value of vi indicates the higher antibonding electron density
in the lowest excited quartet state, i.e. higher metal-ligand bond weakening in the lowest excited
quartet state.
• Rule 1: Thus for the unsymmetrical octahedral complexes, we may say that, in general, the longer
wavelength component of the L} band corresponds to the accumulation of electron density in the
antibonding orbital directed along the weaker field axis. Thus the axis having the lower average
ligand field strength will be labilised more in terms of the dissociative activation. It leads to the
Rule 1, if we assume that all the photochemically excited states will rapidly convert into the
lowest quartet excited state through the different possible ways as shown in Jablonski diagram
(cf Fig. 6.9.5.1). Thus it is reasonable to expect that regardless of the wavelength of irradiation,
the complex will attain the same lowest excited quartet state (i. e. same quantum yield).
• Rule 2: Higher ligand field strength (i.e. more /10) makes, in general, the eg orbitals of more
antibonding character. Thus the ligand field excitation (i.e. t2g ~ eg ) weakens the metal-ligand
bond more where /10 is more. This is why, in general, the quantum yield for the photochemical
reactions passing through the dissociative activation increases with the ligand field strength. This
explains the Rule 2.
Illustration: (i) Anion of Reinecke's salt, i.e. trans-[Cr(NCS)4(NH 3)2]- possess two different types of
axes, i.e. H3N-Cr-NH 3 (stronger field axis) and SCN-Cr-NCS (weaker field axis which experi-
ences the better labilisation). According to Rule 1, it should have the photoaquation of thiocyanate not
NH 3• In fact, it happens so.
trans-[ Cr(NCS)4 (NH 3)2 r (+~:O) [ cr(Ncsh (NH 3)2 (OH 2 )] + NCS-
(ii) In [Cr(NCS)(NH 3 )s]2+, the two axes are: H 3N-Cr-NH 3 (stronger field axis) and
H3N-Cr-NCS (weaker field axis which experiences the better labilisation). In fact, it experiences
the photo-aquation of NH3 which is a stronger field ligand than NCS- (Rule 1, 2).

[Cr(NCS)(NH 3 )st (+~:O) )[ Cr(NCS) (NH 3)4 (OH 2 )J+ + NH 3

(cf Dark or thermal reaction leads to aquation of NCS-).
(iii) In [Cr(NH3)s(N3)]2+, the two axes are: H3N-Co--NH 3 (stronger field axis) and H3N-Co--N3
(weaker field axis which experiences the better labilisation), and NH 3 is a stronger field ligand than N:3.
It leads to the photoaquation of NH3 (Rule 1 and 2).
866 FUNDAMENTAL CONCEPTS OF INORGANIC CHEMISTRY

LF excitation

(~reen. li~ht)
Irradiation

(iv) Photochemical behaviour of the cis-trans isomers of [Cr(en)2(OH)2]+:

N~
Racemisation
H!~j-7i
I Cr I (a)
!/"":
HO- - - - - - - - - - - N

!~
(b)
Substitution
'------------3~ [Cr(en)(OH)2(OH 2)2]+ + en (c)
(aquation)

cis-[Cr(en)2(OH)2]+

Racemisation (a) and isomerisation (b) of cis-[Cr(en)2(OH)2]+ occur through the one-ended
dissociation of ethylenediamine (en) chelate (producing an intermediate of lower coordination number)
followed by the reattachment by the dissociated end of en to the metal centre. Photochemically the en-
aquation and isomerisation reactions (b,c) are important while the predominant thermal reaction is
only isomerisation. Thermal reaction cannot aquate en.
In cis-[Cr(en)2(OH)2]+ the two ligand field axes are:
(en)N-Cr-N(en) (stronger field axis) and (en)N-Cr-OH (weaker field axis). According to
Rule 1, the more labilised axis is (en)N-Cr-OH and according to Rule 2, the (en)N-Cr bond
is labilised more. Thus photoaquation of en (reaction c) and photo-isomerisation (reaction b)
can be explained through the rupture of (en)N-Cr bond. In the corresponding trans-complex, the
weaker field axis is HO-Cr-OH. It predicts (Rule 1) the O-exchange and isomerisation through
the formation of a stereomobile intermediate of lower coordination number. For the trans-compound,
en-aquation is not expected and it has been experimentally verified.
• cis-[Cr(en)2(OH)2]+ (weaker field axis: (en)N-Cr-OH): en-aquation and isomerisation but
no O-exchange.
• trans-[Cr(en)2(OH)2]+ (weaker field axis: HO-Cr-OH): O-exchange and isomerisation but no
en-aquation.
These predictions have been qualitatively verified.
Limitations of the Adamson's empirical rules: There are many experimental findings to contradict
the Adamson's rules. For example, in photoaquation of [Cr(NH 3)s X]2+ (X-= halide or pseudo-
halide), photoaquation occurs along the trans-H 3N-Cr-X axis (Rule 1) and it should give the
trans-[Cr(NH 3)4(OH2)(X)]2+ but this expectation is not always satisfied. Formation of the cis-product
has been explained by considering the stereomobile character of the photochemically excited states of
Cr(III) of lower coordination number.

6.9.6 Photolysis of [M(CN)a]3- and [M(CN)a]4- (M = Mo, W) in Aqueous Solution

The quantum yield (<I» for photolysis of [M(CN)s]3- is greater than 1. To explain this higher value of <1>,
it has been argued for the generation of OH radical (in the primary photochemical process) which
subsequently participates in the reaction. The suggested reaction paths are:
REACTION MECHANISM: ELECTRON TRANSFER REACTIONS AND PHOTOCHEMICAL REACTIONS OF METAL COMPLEXES 867

[M(CN)S]3- +H20~[M(CN)S]4-+H+ +OH

[M(CN)S]3- +OH~[M(CN)S]4-+H+ +!02

2

[M(CN)s]3- +H20+0H~[M(CN)s]4-+H+ +20H

6.9.7 Photolysis of the Oxalato-Complexes, [M(OX)3]3- (M =Fe, Mn, Co)

The said tris-oxalato-complexes undergo the redox decomposition during the photolysis. The proposed
mechanism involving the intermediates M(IV) and M(II) is outlined below.

[MIll (C 20 4)3t + C20 4~[MIV(C204)3r- + C20~-

1
[M"(C 20 4)2r- +2C0 2
The overall process of photolysis of [M(C 20 4)3]3- may be shown as follows:

2[ M(C 20 4 )J 3
- ~2[ M(C 20 4)2J- +2C0 2 +C20~-
The quantum yield (<p) for such photochemical redox decomposition processes depends on the
wavelength of irradiation but it remains more or less constant in the charge-transfer region and it
decreases in the d-d band region. For example, for [Fe(C 20 4h]3-, the <p value (0.4-0.6) is fairly high in
the CT region while the <p value is very small in the region of spin-forbidden d-d band region (ca. ) 650
nm). The higher quantum yield (ep) for the light of shorter wavelength arises due to the fact:
allowed transition in the CT band region, excess energy allows the degraded species [M(C 20 4h]2- and
C 20; to escape away from each other and preventing their recombination. At higher wavelength (i.e.
low-energy light), recombination of the oxalate radical with [M(C 20 4)2]2- is more probable (cage
effect) to reduce the <p value.
Note: • Some of the oxalato-complexes find uses in actiometer. [Fe(ox)3]3- can be used in this pur-
pose. U0 22+ - oxalate system can also be used in acitometer. It may be noted that U0 22+ can cause
photochemical oxidation of different types of organic and inorganic substrates.
=
• The complexes of Co(III), Mn(lll) and Fe(III), i.e. [M(C 20 4)3]3- (M Co, Mn, Fe) experience
the redox decomposition photochemically but the corresponding Cr(III)-complex, i.e. [Cr(C 20 4h]3-
does not experience any such photochemical redox decomposition. The proposed mechanistic paths
involve the participation of intermediates M(IV) and M(II). Thus formation of these oxidation states
should be energetically feasible. In fact, photochemical stability of [Cr(C20 4)3]3- arises due to the fact
that the generation of Cr(II) is not likely. However, the Cr(III)-complex experience the photorecimization.

6.9.8 Photochemical Reactions of the Fe(lI) and Fe(llI) Complexes

• Photolysis of an acidic aqueous solution of Fe(ll) can lead to oxidation of Fe(ll) to Fe(III).