Electronic Spectra of Square-Planar Complexes The Journal of Physical Chemistry, Vol. 82, No.

1, 1978 69

Electronic Absorption Spectra of Square-Planar Chloro-Aqua

and Bromo-Aqua Complexes of Palladium(11) and Platinum(11)

Lars Ivar Elding" and Lars Frlde Olsson

Physical Chemistry 1, Chemical Center, University of Lund, P.O. Box 740, S-220 07 Lund, Sweden (Received August 8, 1977)
Publication costs assisted by the University of Lund

Visible and UV aqueous solution spectra for the square-planar complexes PtClfi(H20)4-n2-n,PdC1,(H20)4-2-n,
and PdBrn(H20)4-2-n (n = 0, 1,2, 3,4) have been recorded and calculated. The difference in blue shift within
each family of spectra when halide is substituted by water is two to three times smaller for the d-d bands than
for the symmetry-allowedhigh-intensity bands. This vatiation of blue shift and the variation of band intensity
due to the different symmetry of the complexes within each series together with previous magnetic circular
dichroism and polarized crystal spectra have made possible unambigous assignments of the bands in the MX?-

- -
spectra (X = C1, Br). Thus, the shoulders at 3.79 pm-l (PtC142-)and 3.03 pm-l (PtBr42-)are probably due to
2az, 2b2gand the shoulders at 2.9 pmJ1 (PdCl?-) and 2.35 pm-l (PdBr4? to 3blg apg,Le., these shoulders
are probably not associated with d-d transitions as often previously assumed. The symmetry-allowed

- -
high-intensity bands in the UV PtCld2-spectrum at 4.65 and 4.34 pm-l (3.73 and 3.37 pm-' for PtBrd2-)are
described as metal-to-ligandcharge transfer transitions 2azU 3alg and 2aZu 2egwhereas the symmetry-allowed
bands in the PdC142-spectrum at 4.50 and 3.74 pm-l (4.05 and 3.02 ym-l for PdBr42-)are described as lig-

-
and-to-metal charge transfer 3bl, 2eu and 3blg bZu, 3e,. The results also suggest that the lB1, 'Alg and
+- +-

lE, lAlg transitions overlap both in the platinum and palladium complexes, Le., the d2zmetal orbital is probably
very close in energy to the degenerate d,, and d,, orbitals. These conclusions are summarized in the simplified
+-

energy level diagrams in Figure 8.

Introduction
Transition assignments for electronic spectra of
square-planar halide complexes of palladium and platinum
have been based on experimental solution spectra,'-'
polarizedg-15 and luminescence16 crystal spectra, and
measurements of circular dichroism (CD4 and MCD3i5).
Crystal and ligand field theory1v2J2J6and MO
have been used for the interpretation of these experiments.
Martin13 has reviewed the literature on the platinum
complexes up to about 1970. However, there are still
several ambiguities concerning the assignments both of the
high-intensity bands in the UV and the less intense d-d
bands in the near visible region.
The high-intensity bands in the UV spectra of both
PdC1:- and PtC1:- have generally been described as
calculations give various results for the order between dZ2
and d,,, d 2. For instance, Chatt et a1.l and Patterson et
a1.16 concrude that d22 has the lowest energy, whereas
Fenske et place d,z above d,,, d,,,. Martin, Tucker, and
Kassman12bdiscuss two alternatives: A, having d,,, d,, >
d,z, and B, which was considered to be the most probable
by the authors, with d,,, d,, = d,z.
Obviously, the results of some of the ligand and crystal
field calculations are strongly dependent on the chosen
assignments for the observed bands in the d-d region,
which is by no means univocal. For instance, the shoulder
at 3.65 pm-l in the crystal spectrum and at 3.79 pm-l in
associated with 3bl, -
the solution spectrum of PtC142- has sometimes been

sometimes with a spin-forbidden charge transfer transi-

-
3alg (dXz-,z dZz)6,8,13,16,18121123
and

ligand-to-metal charge transfer transitions (to 3b$.426>17318,22 tion.12J7 Similarly, the shoulder at 2.9 pm-l in the solution
- -- -
However, Anex and Takeuchi14 recently reported a strong spectrum of PdC1:- has alternatively been described as
out-of-plane polarization for the 4.6-pm-l(1 pm-l = 10 kK) 3blg 3al (d,z-,z dzz),18a mixture of 3b 2b, (d,z.g
band of K2PtC14,whereas the 3.6-pm-' band of K2PdC14
was found to be in-plane polarized. The authors therefore
+-

-
d,,) and 3blg 2eg (d,z-,z d,,, dy,),21;Large transfer
+-

3blg aZg,.' or recently as due to the presence of small

-
concluded that the 4.6-pm-l absorption in the PtC14*-
spectrum is due to 5d,z 6p,, i.e., a transition to 2a2,. This
is not consistent with the previous assignment scheme for
concentrations of dinuclear ~omp1exes.l~
We here report solution spectra for three series of
halo-aqua complexes, viz. PtC1,(H20)4-,2-n, PdC1,-
PtC142- developed by Gray et al.17J8 Simultaneous MO (H20)4-2-n,and PdBrn(H20)4-2-n( n = 0, 1,2, 3,4), which
calculations by Messmer et a1.21 also indicate that the together with previous MCD3v5and p ~ l a r i z a t i o n ' ~ - ~ ~ J ~ J ~
4.6-pm-l band of PtC12- probably is associated with a
transition 8azu 5eg (lEU).(This is equivalent to 2a2,
+-

2eg using the nomenclature of Basch and Gray.ls In the

following text, the energy levels will be denoted according
to ref 18). Accordingly, the band should be in-plane
polarized.
As far as the low-intensity d-d transitions are concerned,
there seems now to be general agreement that the order
both for PdC1:- and PtC1:- is 3bl, (d,z-,z) >> 2bp (d,,) >
2eg (d,,, d,,), whereas the position of 3alg (d,$ still is
unclear. Recent MO calculation^^^^^^*^^ generally support
the order d,,, d,, > d,z, but van der LugtZ0arrives at d,z
> d,,, dyz> dXyThe semiempirical ligand and crystal field
.OO/O
0022-3654/78/2082-0069$01
-
data, might be helpful for the spectral assignments. The
assignments for the MXZ- complexes with Dlh symmetry
can be transferred to the other complexes in the family
MX,(H20)4-,2-n having lower symmetry (cf. Chatt et a1.l).
A comparison of the energies and intensities for corre-
sponding bands in such a series of spectra will furnish a
possibility to check the spectral assignments. For instance,
the stepwise displacement of the d-d bands toward the UV
when halide is substituted by water in MX42- is much
smaller than the corresponding displacement for the
high-intensity bands. Moreover, bands which are sym-
metry forbidden in the Dlh complexes can be allowed in
complexes having lower symmetry, so observed changes
0 1978 American Chemical Society
70 The Journal of Physical Chemistty, Vol. 82, No. 1, 1978 L. I. Elding and L. F. Olsson
500 LOO 350 300 250 230

vf7 20 25 30 35 40 45

Flgure 1. d-d spectra for PtCI,(H20)4-,2-n ( n = 0, 1, 2, 3, 4). The

spectrum for n = 2 represents the equilibrium mixture of cis and trans
isomers (55% cis).
250 240 230 220 210

Figure 3. d-d and first high-intensity bands for the equilibrium mixture
ci~ltrans-PtCI,(H,O)~resolved into its components.

I
12 -

10 -

in intensity might also give useful information.

( n = 0, 1, 2, 3, 4).
Figure 2. High-intensity bands for PtCln(H20)4-n2-n
RCI,(H20)2 has been resolved into cis and trans spectra.
8 - 3 I: 4 2 1 0

Experimental Section
Chemicals and Apparatus. K2PtCI, (Johnson and 6-
Matthey) was the same as used p r e v i ~ u s l y .Solutions
~~ of
platinum(I1) perchlorate and palladium(I1) perchlorate
were prepared by published method^.^^^^ Perchloric acid
(Baker p.a.), hydrochloric acid (Merck p.a.), freshly dis- 4-
tilled hydrobromic acid (Merck p.a.), and water, doubly
distilled from quartz vessels, were used to prepare the
solutions. Perchloric acid was the supporting electrolyte.
The ionic strength was 1.00 M. The hydrogen ion con- 2 -
centration of 1.00 M is sufficient to suppress protolysis
both of palladium and platinum aqua ions.7@Spectra were
recorded a t 25.0 "C using a Cary 15 recording spectro-
photometer and Hellma Quartz Suprasil cells.
PtCI(H20)8t. After equilibration for 75-150 h at 25 "C Figure 4. d-d and first charge transfer bands for PdCIn(H20)4..n2-n( n
spectra for ten solutions having Cpt = 7.18 mM and 0 I = 0, 1, 2, 3, 4). The spectrum for n = 2 represents a mixture of 68%
Ccl I 2.8 mM and seven solutions with Cp, = 4.08 mM and cis, 32% trans.
0 5 Ccl I 1.6 mM were recorded between 400 and 210 nm. 300 250 210
The half-life for the equilibration is about 18 h for Cp, =
4 mM.26 The molar absorptivity for PtC1(H20)3+,cl, was ~,xl0-4/cm-1~-1

obtained from the equation e = eOCPt+ (q - to)Cc1, where

e denotes the absorptivity of the solution and to the molar
absorptivity for Pt(H20)>+, determined p r e v i ~ u s l y . ~ ~
Concentrations of other complexes were negligible.
t r a n ~ - P t C l ~ ( H ~ OSolutions
)~. of Pt(H20)42+(4.12 or
0.412 mM) containing hydrochloric acid (50 mM) were
aged for 75-100 min at 25 OC and their spectra subse-
quently recorded between 550 and 205 nm. The following
reaction to t r ~ n s - P t C l ~ ( H ~occurs
O ) ~ q~antitatively:~~

Pt(H,0),2C -
f c1-
PtCl(H,O): -
+ c1-
fast
trans-PtCl,(H,O), (1) Flgure 5. Charge transfer spectra of PdCln(H20)4-n2-n ( n = 0, 1, 2,
3, 4). The spectrum for n = 2 represents a mixture of 68% cis, 32%
trans.
Consecutive chloride anations of PtC1(H20)3t to cis-
PtC12(H20)2and of t r a n ~ - P t C l 2 ( H ~ to
O )PtC13H20-
~ are ~ i s - P t C l ~ ( H ~ 0Spectrum
)~. for cis-PtC12(H20)2was
slow.26 The half-life for the rate-determining anation of calculated from the spectrum of the equilibrium mixture
Pt(H20)d2' is 9 min for 50 mM chloride.25 of cis- and t r a n ~ - P t C l ~ ( H ~recorded
O ) ~ previously2' and
Electronic Spectra of Square-Planar Complexes The Journal of Physical Chemistry, Vol. 82, No. 7, 1978 71

TABLE I: Wavenumbers, k-'/wm-', and Molar Absorptivities, e,/cm-' M-', for PtC1,(H20)4.,2~n(n = 0, 1, 2, 3, 4 )
Excited
cis-PtC1,- trans-PtC1,- Assignment state
PtC1,'- PtCl,(H,O)- (H,O), (H,O), PtCl(H,O): Pt(H,O),+ (D4h) (D4h)
1.78 (3) -a - - - - d-d singlet -+ triplet
2.10 (17) 2.14 (19) 2.25 (20) 2.25 (10) - 2.57 (10) d-d singlet triplet -+

2.56 (56) 2.61 (48) 2.69 (25) 2.81 (35) 2.85 (25) 3.13 (15) 3blg(dx2-yZ)+ 2bzg(dxy) 'Azg
3.02 (59) 3.14 (107) 3.25 (170) 3.31 (40) 3.43 (87) 3.66 (57) 3b1g (dXz-y2)+ 2,g (dxy, dxz), 'Eg, Big
3a1g ( 4 2 )
3.79 (-400) 4.3 (1500) 4.45 (900) Absent -- - 2a,+ 2bzg 'BlU
4.34 (7200) 4.8 (8000) - - - 2aZu+ 2eg 'Eu
4.65(9050) - - - - - 2aZu+ 3a1g 'A,,
a A dash denotes not observable. Proposed assignments for D4h symmetry (PtCl,'-, Pt(Hz0,)2+) included. Reference
27. Reference 24.
TABLE 11: Wavenumbers, k-'/pm-', and Molar Absorptivities, en/cm-' M-',for PdCl,(H,0),.,2-n (n = 0, 1, 2, 3, 4 )
PdC12(H2 0 )2 Assignment Excited state
PdC1,'- PdCl,(H,O)- (68% cis) PdCl(H,O)+ Pd(H20)42+ (D4h) (D4h)
1.65 (8) 1.71 (10) 1.75 (10) 1.80 (8) 1.86 (2.5) d-d singlet triplet -+

2.11 (161) 2.32 (227) 2.38 (243) 2.46 (175) 2.64 (82.8) d-d bands (cf. Table I) 'Azg,'Eg, 'Big
2.9 (200) 3.18 (800) 3.4 (400) 3.9 (200) - 3b1g+ a2g 'B2,
3.58 (10300) 4.18 (14500) 4.25 (5000)
- - 4.72 (12000) -- 3b1g 3eu, bzu +- 'E,, 'AZU
4.50 (29000) -a 3b,,+ 2eu 'E,
a A dash denotes not observable. Proposed assignments for D4h symmetry included.

TABLE 111: Wavenumbers, k-'/prn-', and Molar Absorptivities, en/cm-' W', for PdBr,(H20),.,2-n (n = 0, 1, 2, 3 , 4 )
PdBrz(H2O)z Assignment Excited state
PdBr,'- PdBr,(H,O)- (86% cis) PdBr(H,O); Pd(H,O),'+ (D4h)
-a - - 1.8 (30) 1.86 (2.5) d-d singlet -+ triplet
1.96 (200) 2.0 (200) 2.3 (400) 2.42 (280) 2.64 (82.8) d-d bands (cf. Table I) 'Azg, 'E,, 'Blg
2.35 (200) 2.52 (1500) 2.7 (250) -3.5 (450) 3 4 , a2g 'B,
I

2.73 (3000) 3.2 (3000) - - +

3b,g 3% b2u
+ A2u
3.02 (10800) 3.67 (15000) 3.75 (6000) 4.38 (14800) - 3blg+ 3eu 'EU, A,
3.65 (6000) - - - - 3blg+ 2eu
4.05 (30000) 4.38 (15000) 4.45 (16000) - - 3b1,+ 2eu 'E,
a A dash denotes not observable. Proposed assignments for D4h symmetry included. The assignments for the bromo-
aqua complexes are uncertain because of spin-orbit and symmetry splitting and mixed cis and trans spectra for n = 2.

the known spectrum of the trans isomer using the equi- 500 400 300 250 210
librium constant K,,, = [cis]/[trans] = 1.2 f 0.1 deter- 2000
mined separately.26
Palladium Complexes. Spectra for equilibrated solu-
tions of palladium complexes were recorded and resolved
as described previously.' 1000
Results and Discussion
Spectra. The spectra are shown in Figures 1-7.
Gaussian analysis gave the results in Tables 1-111. The

A I
suggested assignments have been summarized in the tables. 20 2.5 30 3.5 40 L.5 7
Two separate band systems can be recognized in each yb-'
family of spectra, namely, the high-intensity bands in the Figure 6. d-d and first charge transfer bands of PdBr,(H20)4-,,2-" ( n
UV and the weak (d-d) bands in the UV-near-visible = 0, 1, 2, 3,4). The spectrum for n = 2 represents a mixture of 86%
spectral region. All these bands are displaced toward the cis, 14% trans.
UV when the halide ligands are exchanged for water, but 3 _ , 4?0 , 350 , 3?0 , , , , 2fO
the blue shift is two to three times smaller for the d-d &nx10-4/crn-1M-1 h lnrn
bands than for the high-intensity bands. The spectra for
the chloro-bromo complexes PtC14-nBr2- ( n = 0, 1, 2, 3,
4) reported elsewhere28display similar characteristics. The
d-d bands of PtC1:- at 2.56 and 3.02 pm-l are displaced 2
to 2.42 and 2.72 ym-' in the PtBr2- spectrum, whereas the
high-intensity bands a t 3.79, 4.34, and 4.65 pm-I are
displaced about three times more, to 3.03, 3.37 and 3.73
Km-l, respectively, in the PtBr42-spectrum. This means
that the energy differences between the filled and excited
one-electron energy levels which give rise to the high-
intensity bands are much more affected by the nature of
the ligands, than are the corresponding energy differences
for the d-d bands. Using the MO-LCAO language, this Flgure 7. Charge transfer spectra for PdBrn(H20)4-n2-n ( n = 0, 1, 2,
is equivalent to saying that there is a larger mixing between 3,4). The spectrum for n = 2 represents a mixture of 86% cis, 14%
those metal and ligand AOs which give rise to the energy trans.
72 The Journal of Physical Chemistry, Vol. 82, No. I , 1978 L. I. Elding and L. F. Olsson

TABLE IV: Absorption Spectra of PtC1,2-(aq) and Single-Crystal K,PtCl,(s) at Room Temperature
PtCl,' -( aq lb
K,PtCl,(s)
E/
cm-' E/cm-' MCD
k-'/pm-' M-' A-'/pm-' Me' Polarzn'" Rep termd Assignment Excited state

i
1.78 3 1.73 5 xy 10
2.02 20 Z 10,12b
2.10 17 2.04 17.5 xy 10, 12b
2.34 9(?) xy 12b
2.37 5 Z 12b
2.56 56 2.57 45, 62 xy 10,12b B
3.02 59 2.85 57, 74 XY 10,12b A
2.93 70,101 z 10,12b
3.79 -400 (3.65) ? 10 B
4.34 7200 (-4.5)e (XY) 14 A
4.65 9050 4.41 32100f z 14
'"x y denotes in-plane polarization, z out-of-plane polarization. cf. Table I. Cf. also ref 11,which gives values at 5 K.
' ~ p 4415.) According to ref 1 4 this
References 3 and 5. e Estimated from ref 14, Figure 1. (Cf. also the d i s c ~ s s i o non
crystal E should be divided by 3 for comparison with the solution value.

TABLE V: Absorption Spectra of PdC1,2-(aq)and Single-Crystal K,PdCl,(s) at Room Temperature

-PdC1,z-(aq)b K,PdCl,(s)
e/cm-' e/cm-' MCD
A-'/pm-' M-' k-'/pm-' M-' Polarzn'" Ref term Assignment Excited state
1.65 8 1.70
(1.80)
7
(19)
10, 15d
10, 15d I
2.11e (2.00) (67) 10, 15d A
161 2.26 128 10, 15d
2.30 80 10, 15d
2.9 200f (2.95) (67) 10
3.56 10300 3.68
3.74
14000
388 l4
15d
B 1
4.50g 29000 4.51 27600 14 A
a x y denotes in-plane polarization, z out-of-plane polarization. Cf. Table 11. Reference 5. Reference 1 5 gives
values at 1 5 K. e Asymmetric band, cf. ref 7, Figure 9. f McCaffery et ala5and Rush et al.15report E N 500 cm-l M-'.
Rush et aiel5report a band at 4.078 pm-l with E = 900 cm-' M-'.

levels connected with the high-intensity bands than there
is between those AOs giving rise to the levels for the d-d
bands. Thus, the MOs 3alg,2eg,2bzg,and 3bl, can probably
be considered to be rather pure metal d orbitals. This is
contrary to the conclusions from the MO calculations by
Messmer et al. (ref 21, pp 2852,2853) but agrees with the
calculations by Cotton and Harris.lg
Shoulders. It appears from Tables 1-111 that the dis-
placements of the shoulders at 3.79 (PtClt-), 2.9 (PdClt-),
and 2.35 pm-l (PdBr42-) for the stepwise substitutions of
the halides by water is about the same as the corresponding
changes for the known symmetry-allowed high-intensity
bands. It is therefore not very likely that these shoulders
and the corresponding shoulder for PtBrd2-at 3.03 pm-'
(cf. ref 28) are d-d bands as has often been as-
s ~ m e d . It ~is much ~ ~more ~ probable
~ ~ ~that~ they , ~ ~band
~ are
due to symmetry-forbidden transitions of the same type
as the high-intensity bands, which has previously been
suggested by Saito et al.4 Further support to this as-
signment is given by their relatively large intensities and
by the variation of these intensities with the symmetry of
the complexes within the series MX,(H20)4-n2-n (vide
infra).
McCaffery5 and their co-workers show that this band
contains an A term connected with the transition from the
degenerate level 2eg (d,,, dy,) to 3blg (dx2-y2),but cannot
exclude the possibility that the band also contains 3b1,
3alg (cf. McCaffery et p 5732). The polarization
-
measurements reviewed in Tables IV and V, however,
--
suggest that the 3.02-pm-' band might contain both these
transitions. The 3blg 2egtransition will be out-of-plane
( 2 ) polarized and the 3blg 3alg in-plane (xy)polarized,
if they are allowed via E, vibrations (cf. Chatt et ala1).In
fact Day et al.,1° Mortensen,ll and Martin et al.12b,16 report
the existence of two polarized components at about 2.85
( x y ) and 2.93 pm-l (z)10,11p12bfor K2PtC14 crystals and at
about 2.26 (xy)and 2.30 pm-l (2)10915for KZPdCl4crystals
(cf. Tables IV and V). They correspond to the 3 . 0 2 - ~ m - ~
~ of~ PtC12-
~ ~ solutions
~ ~ and to the asymmetric 2.11-pm-l
band of PdC142-solutions.
So we conclude that the broad absorptions at 2.11
-
(PdC142-)and 1.96 pm-l (PdBr?-) contain all the three
-
singlet singlet d-d transitions, whereas the band at 3.02
1m-l (PtClt-) contains the two singlet singlet transitions
-
from 3al, (d,z) and 2eg (d,,, dyz)and the 2.56-pm-l band
(PtCL2-) the transition 3bl (d,z_?z) 2bzg(dxy).Similarly,

-
d-d Bands. The exclusion of the above-mentioned
-
shoulders as due to the 3blg 3alg (d,e 2 d,z) transition
removes the main difficulty with the d m t i n , Tucker, and
KassmanlZbalternative B for the assignment of the d-d
bands of PtC1,2- (cf. also Patterson et a1.,16 p 2875).
The two levels 3alg (d,z) and 2eg (d,,, d are probably
so close in energy that the transition from goth these levels closer to the filled levels in the palladlum complexes than
to 3bl (d,z-yz) are contained within the 3.02-pm-' band of
P t C l F solution spectrum. The MCD results by Martin?
due to 3blg -
the band at 2.42 pm-l in t i e PtBr42-spectrum should be
2bzg and the band a t 2.72 pm-l should
contain both transitions from 3al, and 2e to 3blg (cf. ref
28, Table X). The splitting of the filled Jlevels (d,z, d,,,
dyz,dxy)can be concluded to be smaller in the palladium
complexes than in PtClt-, and the d1f-y2orbital should lie
in PtC142-,since the transitions have lower energies in the
former complexes. These conclusions are summarized in
Electronic Spectra of Square-Planar Complexes
hlgh.lntenrity
I I I ,
34, i 2 e u
PtC1:- PdCI:'
Flgure 8. Suggested simplified energy level diagrams for PtCI4*- and
PdC1,'- complexes in aqueous solution. Notation of ener y levels
according to ref 18. The experimental wavenumbers in pm (1 pm-'
= 10 kK) have been included. Symmetry-forbidden transitions have
been marked with dashed arrows and allowed transitions with fulldrawn
arrows. The diagram for PtCI4'- should be applicable for PtBr,'- also,
and that for PdC142-for PdBr4'-.
the energy level diagrams in Figure 8.
High-Intensity Bands. Anex and Takeuchi14 concluded
-
that the intense absorption in the PtClt- spectrum at 4.65
pm-l is due to a metal 5d 6p transition (2azu 3alg),
in agreement with the proposed assignments by Chatt et
a1.l and by J o r g e n ~ e n .If~ ~we assume that the shoulder
a t 4.34 pm-l and the previously discussed shoulder at 3.79
pm-' in the PtC1,2- spectrum are also associated with
transitions from the metal d levels to 2azU,we arrive at the
simple energy level diagram for PtC1d2- in Figure 8.
The bands at 4.65 and 4.34 pm-' are symmetry allowed.
The shoulder at 4.34 pm-l contains a MCD A term5 which
is compatible with the assignment 2az, -
2eg. The two
bands a t 4.65 and 4.34 pm-' differ by 0.31 pm-' whereas
there is no observable difference between the two corre-
sponding d-d transitions from 3alg and 2eg at 3.02 pm-'
(cf. Figure 8). This might be due to differences both in
interelectronic repulsion and configurational interaction
depending on whether the electron is excited to the 2az,
or 3blg level.
The shoulder at 3.79 pm-' is symmetry forbidden but
vibronically allowed via a Bz vibration (cf. Chatt et al.'
concerning vibrational modess. The transition must then
be out-of-plane ( 2 ) polarized, but unfortunately no data
on its polarization have been published so far. This
transition is also symmetry forbidden for all the mixed
complexes except cis-PtClz(HzO)z,which belongs to the
symmetry group CZv(C2/').The presence of a maximum
a t 4.45 wm-l for cis-PtClz(HzO)zand the absence of any
corresponding absorption for trans-PtClz(HzO)z (cf.
Figures 2 and 3 and Table I) supports our assignment.
This band is also strong ( E = 1500 cm-l M-l) for PtC13H20-,
which belongs to Czu(Ci),One explanation might be that
the transition is allowed via a B1 vibration, which corre-
sponds not only to the BZgbut also to the E, vibration in
- -
PtCl?-. Corresponding assignments for the high-intensity
bands of PtBr4'- at 3.03 (2azu 2bzg), 3.37 (2azu 2eg),
and 3.73 pm-' (2azu 3alg) can be made.28
The assignments for the two symmetry-allowed tran-
sitions at 4.65 and 4.34 pm-' (and also for the 3.02 pm-l
d-d band) are further supported by a comparison of so-
lution and crystal spectra, see Table IV. Because of
electrostatic effects in the solid state, the energy of the 3alg
(d,4 orbital will be higher in the crystal than in aqueous
solution both relative to the in-plane d orbitals (including
The Journal of Physical Chemistry, Vol. 82, No. I, 1978 73
3blg) and to the 2az, orbital, a t least if the latter is
composed mainly of ligand p orbitals (vide infra).
Transitions from 3alg should therefore be expected to show
a red shift in the crystal spectrum. Accordingly, the
4.65-pm-' solution band is displaced to 4.41 pm-l in the
crystal spectrum and one of the components of the
3.02-pm-' band to 2.85 pm-l, whereas the other bands are
much less affected.
As far as the palladium complexes are concerned, the
-
associated with 3blg 2e, ('E, -
4.50- (PdC142-)and 4.05-pm-l (PdBr42-)bands have been
-
'Alg) and the 3.58-
bzu (lEl, 'Azu -
(PdClt-) and 3.02-pm-l (PdBrt-) bands with 3blg 3e,,
lAlg) in accordance with previous as-
signments by J$rgensen,22Basch and Gray,18 and Rush et
D a1.15
A comparison of the high-intensity bands in solution and
crystal spectra (see Table V) shows that the position of
these bands are much less affected than the bands of
-9 PtC12- at 4.65 pm-l (and 3.02 pm-l), cf. Table IV. This
is consistent with the description of the bands in the
PdCIt- spectrum as due to in-plane transitions.
We have p r e v i o ~ s l yassociated
-
~ ~ ~ ~ the shoulders a t 2.9
(PdClZ-) and 2.35 pm-l (PdBrt-) with 3blg aZg. If this
transition is allowed via an E, vibration, it will be in-plane
(xy) polarized in the crystal spectrum, as was observed
- -
experimentally by Day et al.1° The out-of-plane ( 2 ) po-
larized 3blg bzUtransition found by Rush et all5 in the
crystal spectrum of KZPdCl4a t 3.74 pm-' (cf. Table V)
cannot be identified with the shoulder at 2.9 pm-l in the
solution spectrum, since it differs too much in wave-
number.
-
The transition 3blg aZgis symmetry forbidden for
PdXt-, Pd(HzO)t+,and trans-PdXz(HzO)zbut allowed
for the other complexes in the series PdXn(H20)4-n2-n.
Accordingly, the shoulder develops into a peak for
PdCl3HZ0-, PdC12(H20)z(68% cis), PdBr3HzO-, Pd-
Br2(Hz0)z(86% cis), and PdBr(HZ0l3+,cf. Figures 4 and
6.
-
Since it has lower energy than the allowed 3blg 3e, -
However, the assignment of this shoulder is tentative.
(metal dXz+ ligand p,) transition at 3.58 pm-' (PdC14z-)
it is reasonable to assume that the lowest one-electron
energy level for the 2.9-pm-' (PdCI?-) shoulder is also
composed of ligand p, orbitals (cf. Basch and Gray,la
Figure 1). We have assumed that this orbital is a.29simply
because some MO calculations18J0a~21 place it highest in
energy among the MO set built from ligand pn orbitals.
The energy level diagram in Figure 8 summarizes these
conclusions for PdC1,2-, and should also be applicable to
PdBr42-.
As far as the symmetry-allowed bands of the mixed
chloro and bromo aqua complexes of palladium are con-
cerned, it should in principle be possible to correlate them
with corresponding bands in the PdX42-spectrum, This
-
is complicated by symmetry splitting of transitions to
degenerate states (lE, lAlg in PdCIZ-, cf. Table 11) and,
in the case of the bromide complexes, by spin-orbit
splitting. Moreover, the spectrum of PdX2(H20)2rep-
resents a mixture of the cis and trans spectra, which cannot
+ be so easily resolved as the PtC12(H20)2 spectrum because
of the rapid reactions rates of the palladium complexes.
The shoulders at the low-energy sides of the symmetry
- -
allowed bands in PdBr42- are most reasonably due to
singlet triplet transitions (3E, lAlg).15
The high-intensity bands blue shift in a strikingly similar
manner in going from PtC1,2- to Pt(H20)42+and PdC142-
to Pd(H20ld2+.This is most simply explained if the MO
levels 282, in PtCldZ-and 2e,, 3e, in PdC142-are assumed
74 The Journal of Physical Chemistry, Vol. 82, No. 1, 1978 Yusuke Yasuda and Masaaki Saeki

to be predominantly ligand orbitals. Since the highest (6) W. R. Mason and H. B. Gray, J. Am. Chem. Soc., 90, 5721 (1968).
occupied levels 3alg, 2eg, and 2bZgand the lowest unoc- (7) L. I. Elding, Inorg. Chim. Acta, 6, 647 (1972).
(8) J. L. H. Batiste and R. Rumfeldt, Can. J. Chem., 52, 174 (1974).
cupied level 3bl, are mainly metal d orbitals, the high- (9) D. S.Martln and C. A. Lenhardt, Inorg. Chem., 3, 1368 (1964).
intensity bands in the palladium spectra might be de- (10) P.Day, A. F. Orchard, A. J. Thomson, and R. J. P. Williams, J. Chem.
scribed as ligand-to-metal charge transfer, and those in the Phys., 42, 1973 (1965).
(11) 0. S. Mortensen, Acta Chem. Scand., 19, 1500 (1965).
platinum spectra as metal-to-ligand charge transfer bands.

--
(12) (a) D. S.Martin, M. A. Tucker, and A. J. Kassman, Inorg. Chem.,
Perhaps the charge-transfer bands of PtC1:- might have 4, 1682 (1965); (b) ibid., 5, 1298 (1966).
some d p character as previously ~ u g g e s t e d , ~but
J ~a~ ~ ~ (13) D. S.Martin, Inorg. Chlm. Acta Rev., 5, 107 (1971).
pure d p transition should blue shift much less within (14) B. G. Anex and N. Takeuchi, J. Am. Chem. Soc., 96,441 1 (1974).
(15) R. M. Rush, D. S. Martin, and R. G. LeGrand, Inorg. Chem., 14, 2543
the series than observed, as a T donor ligand should de- (1975).
stabilize both 2aZuand the filled d orbitals. (16) H. H. Patterson, J. J. Godfrey, and S.M. Khan, Inorg. Chem., 11,
2872 (1972).
Acknowledgment. Our thanks are due to Fil. mag. (17) H. B. Gray and C. J. Ballhausen, J. Am. Chem. Soc., 85, 260 (1963).
(18) H. Basch and H. B. Gray, Inorg. Chem., 6, 365 (1967).
Ingegerd Lind for experimental assistance and to the (19) F. A. Cotton and C. B. Harris, Inorg. Chem., 6, 369 (1967).
Swedish Natural Science Research Council for financial (20) (a) W. T. A. M. van der Lugt, Chem. Phys. Leff., 10, 117 (1971);
support. (b) Int. J. Quant. Chem., VI, 859 (1972).
(21) R. P.Messmer, L. V. Interrante, and K. H. Johnson, J . Am. Chem.
Soc., 96, 3847 (1974).
References and Notes (22) C. K. Jtrgensen, Prog. Inorg. Chem., 12, 130 (1970).
(1) J. Chatt, G. A. Gamlen, and L. E. Orgel, J. Chem. Soc., 486 (1958). (23) C. K. Jtrgensen, "Orbitals in Atoms and Molecules", Academlc Press,
(2) R. F. Fenske, 0. S.Martin, and K. Ruedenberg, Inorg. Chem., 1, New York, N.Y., 1962, p 114.
441 (1962). (24) L. I. Elding, Inorg. Chim. Acta, 20, 65 (1976).
(3) D. S. Martin, J. G. Foss, M. E. McCarville, M. A. Tucker, and A. J. (25) L. I. Elding, Proc. Int. Conf. Coord. Chem., 77th, 39 (1976).
Kassman, Inorg. Chem., 5, 491 (1966). (26) L. I. Elding, Acta Chem. Scand., 24, 1527 (1970).
(4) H. Ito, J. Fujha, and K.Saito, 8ulL Chem. SOC.Jpn., 40, 2584 (1967). (27) L. I. Elding, Acta Chem. Scand., 20, 2559 (1966).
(5) A. J. McCaffery, P. N. Schatz, and P. J. Stephens, J . Am. Chem. (28) L. I. Elding and A,-B. Groning, Chem. Scr., 11, 1 (1977).
Soc., 90, 5730 (1968). (29) C. K. Jtrgensen, private communication.

Kinetic Details of a Gas-Surface System by the Frequency Response Method

Yusuke Yasuda" and Masaakl Saekl

Faculty of Literature and Science, Toyama University, Toyama 930, Japan (Received May 2, 1977)

Adsorption-rate spectra of an ethylene-on-zincoxide system maintained at -70 and -20 " C were observed by
the frequency response method at equilibrium pressures between 4 X and 1.8 Torr. The pressure dependence
of the spectra stemming from two kinds of surface species, termed I11 and I1 in an earlier paper, was interpreted
in a five parameter model; a kinetic equation, (d/dt)Aj = ka6)PNse)(1 - flj) exp(-gjSj) - kdb)NS6)flj
exp(hjflj),was
postulated for each individual surface species j, of which the amount is denoted by Aj and the coverage 0, is
defined as Aj/NsU). All constants in the equation, kae),kd'), N s ~gj,, and hj, were determined according to a
theoretical procedure at each equilibrium temperature; a slight dependence of the constants on temperature
was found and discussed with the Fermi-Dirac distribution for AJT,). Conclusions of hj >> gj 0 for both
species indicate that repulsive forces acting between each kind of the admolecules affect the desorption rate
-
but not the adsorption.

Introduction surface species j; NsG), the number of sites available for

In an earlier paper1 the ethylene-on-zinc oxide system adsorption; k>) and kd8 are rate constants for adsorption
maintained at -20 OC has been investigated, where the and desorption, respectively; and Sj is the coverage defined
kinetic behavior for a t least two kinds of surface species bY
of ethylene has been found to be described by the ej = A , / N ~ (2)
Langmuir equation with sufficient accuracy. It is thought
to be of further interest to study the temperature de- The equation improperly2 termed Becker-Zeldovich has
pendence of the kinetic constants in the equation. been derived from the theory of rate processes by Higuchi,
However, forces acting between admolecules which are Ree, and E ~ r i n g .Though
~ the Elovich equation
neglected in the Langmuir model could not be overlooked
at lower temperatures. (d/dt)A = a exp(-aA) (3)
A kinetic equation taking into account these effects with
the additional constants gj and hj (eq 1)was postulated, where a and a are constants, is known to have the most
general a p p l i c a t i ~ nit, ~may
~ ~ ~be~included in a particular
(d/dt)Aj = kaj)PN&j)(l - ej) exp(-gjej) - case of eq 1. The second term in eq 1 is also reported to
k,(j)Ns(j) 8 exp ( h 8 ) (1) give a good representation of the rate of desorption in
many cases of chemi~orption.~
therefore, instead of the Langmuir equation for each in- In the present article a method is shown for determining
dividual surface species. Here Aj denotes the amount of the five constants in eq 1 from data on the frequency
0022-3654/78/2082-0074$01 .OO/O 0 1978 American Chemical Society