3246 PATRICK

LM.HEFRY Vol. 86

[COSTRIBUTIOS F R O M THE RESEARCH

CENTER, HERCULES
P O W D E R COMPANY, WILMINCTOX 99, DELAWARE]

Kinetics of the Oxidation of Ethylene by Aqueous Palladium(I1) Chloride

h l . HENRY
BY PATRICK
RECEIVED 24, 1964
FEBRUARY

The oxidation, C2HI +PdClp +

HpO + CHjCHO Pdo + +
2HC1, studied in an aqueous HC104-NaC104
system, was found to consist of a n initial rapid ethylene uptake followed by a slow reaction which is first order
in palladous ion and strongly inhibited by chloride ion. The volume of gas initially taken up decreased as the
chloride ion increased, this chloride dependence being consistent with t h e formation of a n-complex, PdClr-2 +
C& [PdC13C2H4] - +
C1-. The rate expression of the slow reaction was -d[CiHa]/dt = k[PdC13CzH4-]/
[ C l - ] [ H + ] for the ranges [Cl-] = 0.1 to 1.0 M, [ H + ] = 0.04 to 1.0 M,and [ P d f 2 ] = 0.005 t o 0.04 M . Only
a secondary isotope effect was observed for C2D,. Increasing ionic strength increased the rate until p = 0.4.
Further increase in p decreased the rate. From the variation of k with temperature, values of AH* = 19.8
kcal. and A S * = -8.7 e . u . were calculated. X mechanism involving the rearrangement of a hydroxo A-com-
plex [PdC12(0H)C2Hr]-to a u-complex consistent with the salt and isotope effects is proposed.

Introduction ladous chloride was detected under conditions of high

Metal ions of the platinum and palladium groups acid and chloride concentration. However, no for-
oxidize olefins only to carbonyl compounds', whereas mation constants could be measured under the usual
mercury (111, thallium(II1) .I and lead(1V)j produce
~
reaction conditions.
both carbonyl compounds and glycol derivatives6 Results
This difference in products may result from the ability At low chloride ion concentration (<0.2 31)the rate
of the platinum metals to react via a a-complex with- of ethylene uptake was mass-transfer controlled when
out proceeding through the u-bonded intermediate creased flasks with magnetic stirring bars were used.
suggested for the other oxidation^.^ On the other However, when a high speed reactor especially de-
hand, different modes of decomposition of a common signed for gas-to-liquid transfer was employed, the re-
u-bonded intermediate may be involved. Both X - action was found to consist of a very rapid initial ethyl-
bondedlJ and u-bondedg intermediates have been ene uptake followed by a slower ethylene absorption.
postulated for the oxidation of ethylqne to acetalde- The volume of ethylene initially taken up exceeded
hyde by palladous chloride in aqueous solutions. This that required to saturate the solution with ethylene.
study was undertaken to clarify the mechanism of this This volume of ethylene taken up in excess of solu-
reaction, especially in regard to differences between bility requirements was found to be unaffected by acid
it and other metal ion oxidations. concentration but decreased as the chloride ion con-
Recently, several studies of the kinetics of the centration increased.
palladous ion oxidation of olefins have been reported. Since the net initial uptake decreased with in-
The ethylene oxidation was found to be first order in creasing chloride ion, it seemed reasonable to assume
ethylene and palladous ionlo$" and inhibited by pro- that the initial reaction can be represented by the
tonslo and chloride ions. T h e proton inhibition equilibrium17
was first order, while the rate depended on the inverse K
square of the chloride ions. Propylene obeyed the PdClr-' + CzHi _r (PdC13CzHd)- + C1- (1)
same rate expression13 while the oxidation of cyclo- I
hexene to cyclohexanone displayed a second-order
chloride inhibition but no acid inhibition.14 The ethyl- The values of K calculated on the basis of this equi-
ene oxidation displayed an isotope effect, k H i k D , of librium are listed in Table I at a constant ionic'strength
4.05 when the reaction was run in DpO.I5 In one of 2 . The value of K varies less than 5% even though
study16 a-complex formation between olefin and pal- the acid concentration is varied by a factor of 5.
(1) J Smidt, et ai.,Angew C h e m . , 71, 176 (1959). TABLEI
( 2 ) J. Smidt, el ai.,Angew Chem. fntevn E d . Engi., 1, 80 (1962). CALCULATIOX
OF EQUILIBRIUM FROM ITITIAL
CONSTANTS
(3) G. F. Wright, A n n . :V Y . A c a d . Scz, 66, 436 (1937) ETHYLESEUPTAKE^
(4) R R . Grinstead, J Ora Chem., 26, 238 (1961).
( 5 ) R Criegee, Annew Chem , 70, 173 (19a8). [ (PdC13-
(6) I n addition, these metal ions also give allylic oxidation with some Run [HClOa] [CI-I CzHd -1 [PdCld-*l [CzHdI' K
olefins. See, for instance, C . B. Anderson and S . Winstein, J . Org. C h e m . , 1 0.2 0 . 0 8 5 0 0033 0.0057 2.78
17.6
28, 603 (1963). 0077 2.67 17.6
2 2 182 0020
( 7 ) H J. Kabbe, A n n . , 666, 204 (1962).
( 8 ) I. I. Moiseev, M . N. Vargaftik, and Ya. K . Sirkin, Dokl. A k a d . X a u k 3 2 ,184 ,00175 ,00725 2.67 16.8
S S S R , 130, 821 (1960). 4 .2 ,383 ,000905 ,00805 2 61 17 2
(9) J Halpern, Abstracts, 141st National Meeting of the American 16 1.0 ,187 0016 ,0056 2.96 17.9
Chemical Society. Washington, D. C . , March, 1962, p. lOQ.
(10) M S Vargaftik, I 1. Moiseev, and Ya. K . Sirkin, Doki. A k a d Average 1 7 . 4 i 0 . 4
.Vauk S S S R , 147, 399 (1962) * A11 concentrations are in moles/l., except for [CZHI]which is
(11) K. Teramoto, T . Oga, S . Kikuchi, a n d M I t o , Y u k i Gosei K a g a k u moles X l O $ / l .
K y o k a i S h i , 21, 298 (1963).
(12) M N. Vargaftik, I I. Moiseev, and Ya. K Sirkin, ISIJ.A k a d . S a u k X plot of log ( V , - V ) v s . time for the residual
S S S R . Old K h i m . S a d ? , 1147 (1968)
( 1 3 ) T Dozono and T Shiba, B ~ i l J, a p a n Pelyol fnsl., 5 , 8 (1983). reaction is linear until chloride ion inhibition becomes
(14) R.f N Vargaftik, I. I . hfoiseev, and Ya. K Sirkin, Dokl. A k a d . S a u k significant, indicating a first-order reaction. Since
S S S R , 139, 1:3U6 (1961).
(1.7) I I hroiseev, X I S Vargaftik, and Ya. K Sirkin, Ize. A k a d . .Yank, (17) T h e assumption t h a t the palladous ion is present almost entirely as
O l i i . Khzin .\auk SSSR,1144 (1963). PdClr-2 a t the chloride ion concentration used in this work is justified by the
(16) I. I . Sloiseev, X I . S Vargaftik. and Ya K Sirkin, Doki A k a d S a u k formation constants of H . A Droll, B. P Block, and W . C Fernelius, J .
S S S R , 152, 147 (1963). Phys. Chem., 61, 1000 (1937).
xug. 20, 1964 OXIDATION B Y AQUEOUSPALLAI)IUM(
OF ETIIYLENE 11) CIILORIDE 3247

5.0
A

-
hl
0

X
--
0.

c X
I

i- 2 . 5
:
rn
-
U
Y I
L L

0 0
U U
Y Y

0
5 10 15 20 25
l/[Htl.
Fig 2.--\ariation of k,,,[CI-] with l / [ H f ] at various chloride
0 5 IO 15 ion concentrations.
l/[cl-l.
Fig. l.--\ariation of k,,, with l / [ C I - ] a t constant acid concen-
tration (0.2 M ) .

a total of 1 mole of ethylene was always consumed

per mole of Pd(I1) initially present, these plots repre-
-3.25
i.
sent the decrease in Pd(1I) concentration with time.
Thus the slower reaction is first order in palladous ion.
The first-order rate constants, kexp, for this reaction
were found to decrease with increasing chloride ion -3.75 I
0 0.5 1 .o 1.5 2.0
concentration. Such a decrease is to be expected if
I is the reactive species CC.
Fig. 3.-Variation of k with ionic strength: 0 , varied by addi-
-d[C*H,]/dt = kc,,[I] = tion of NaCl or SaClOa; 0, p varied by addition of HCIOI.

k,,,K [PdCL-2] [CJ&]/ [Cl-] (2) Results of a series of runs a t various ionic strengths
are plotted in Fig. 3. Lower ionic strengths were in-
Correcting the values of kexp to k,,, by eq. 2 will accessible because the reaction was too rapid to measure
cancel out any chloride ion inhibition by eq. 1 and k,,, a t chloride ion concentrations below 0.1 M . These
should be constant with changing chloride ion if this results are in agreement with those of Vargaftik,
is the only chloride inhibition. However, as Fig. 1 et a l . , l n who found a decrease in rate with increasing
illustrates, k,,, varies linearly with 1/ [Cl-] a t constant ionic strength a t ionic strengths over 0.7. The values
acid concentration, indicating another first-order of K for these runs increased as the solubility decreased,
chloride inhibition. but the value of K defined as
The hydrogen ion dependence on rate was found by
plotting the product k,,, [Cl-] at various chloride ion
K = [PdC13CzHd-] [Cl-]/ [ P ~ C ~ I - ~ ] P C(4)
~H,
concentrations us. 1 / [ H + ] . If there is no acid de-
pendence, the product should be constant but, as Fig. where the P c ~ His, expressed in atmospheres (unity for
2 shows, there is a linear dependence indicating first- all the runs in Fig. 3), remained essentially constant a t
order inhibition by acid. Thus, the complete rate
expression is
*
0.047 O.OO6 mole/l. atm.
Average values of K and k at 15, 25, and 35 are
listed in Table 11. A plot of log k vs. 1/T gave a
_ d [C2H,] -_ kD1 -
-~ straight line. From the slope of the line values of AH*
dt [C1-l[H+l = 19.8 kcal. and A S * = -8.7 e.u. were calculated.
kK[PdC14-] [C2H4] A plot of log kK vs. 1/T did not give a straight line.
(3)
[C1-I2 [H 3 TABLE
I1
EFFECT ON K AND k:
OF TEMPERATURE
where the average value of k is 2.03 f 0.2 X
Temp,
M 2 set.-'. O C [ C ~ H IX
] 108 K* k , C MZ sec - 1 X 10
The first-order dependence on ethylene concentra- 15 3 05 1 8 7 f l 4 0 53 f 0 08
tion was confirmed by running the reaction in a 25 2 67 1 7 4 f 0 4 2 0 f 2
constant volume reactor. A t constant chloride and 35 2 25 9 7 f 1 5 58 f 6
acid concentrations under conditions where the con- p = 2 0 b Average of a t least three runs c Average of a t

centration of I is small, the reaction was shown to least five runs

be first order in palladous ion and first order in ethyl-
ene, as predicted by eq. 3. The average value of k
calculated from these data (2.04 X M 2 sec.-l)
agreed well with those obtained in atmospheric pres-
sure runs.
The isotope effect was determined by measuring the
value of k for
~ C2D4 using the constant volume re-
actor and assuming K is the same as for the undeute-
rated material. The average value of K D for three
3248 M. HENRY
PATRICK
runs was 1.9 k- 0.1 X Mzsec.-l. This cor-
responds to an isotope effect k ' H l k ' D of 1.07.
The agreement between the rate constants found in
this work and those found by Vargaftik, et a1.,lfl l z , l 5
is usually within 25-75y0 for the chloride and acid
concentrations (their kz is equivalent to the product
k'K). This agreement is excellent considering the
differences in ionic strength of the reaction mixtures.
Using high acid and chloride concentrations to stop
the oxidation, these same workers16 measured 9-
complex formation and claim to have measured equi-
libria corresponding to eq. 5 and 6. At 13.4' they re-
ported values of 16.3 for K1 and 0.4 for K 2 . However,
in the present work (see Table I) constant values of K 1
were obtained a t 25' presuming that only the first
equilibrium is taking place to any extent. Treating
our data in the same fashion as these workers gives
K S = 0. Even allowing for experimental error Kz
would be less than 1W2. These workers maintained
constant ionic strength by replacing HCl with HCIOl
and varied their HCl concentration from 1 to 4 -11.
Over this range the principle of constant ionic strength
cannot be expected to hold and their apparent Kz
probably results from the change of K1 with chloride
ion concentration.
Discussion
As concluded by previous workers, l 1 7 l 2 the chloride
inhibition is consistent with the prior formation of an
aquated palladium dichloride 9-complex.
Ki
PdClr-' + C2H4 [PdC13C2Ha]- + C1- (5)
I sistent with the much greater coordinating power of
KZ
I + Hz0 [PC~C~~(H~O)C
C1-
~H~] + (6)
I1
The experimental technique used in this study per-
mitted the measurement of K1. I t was found to
have a value of 17.4 a t 25' and 1 = 2.0. [PtCl3HzO]-
and [PtC13CZH4]- have similar value^^^^^^ of the equi-
librium constant for the equilibrium corresponding to
eq. 6. Thus, since palladous ion has even a smaller
trans effect than platinous ion,*O a good estimate for
KS would be the K of the corresponding equilibrium for
[PdC13H?O]-. This value is ca. l o e 3 M."
The proton inhibition indicates that I1 reacts further
either by attack of hydroxide ion or by dissociation
of a proton from I1 to give a hydroxo species (111).
K8
I1 + H20 [PdC12(0H)C2H4]- H 3 0 + + (7)
111
The salt effects are consistent with either path since
both the ionization product of waterz1 and the ioni-
zation constant of neutral weak show this
(18) D. S . M a r t i n , J r . , and R J. Adams in "Advances in t h e Chemistry
of t h e Coordination Compounds," S. Kirschner, E d , T h e hlacmillan C o ,
S e w York, N. Y . , 1961.
(19) I Leden and J C h a t t , J Chem. S o t , 2936 (1935).
( 2 0 ) 1: Basolo and I? G Pearshn in "Progress in Inorganic Chemistry,"
F. A . C o t t o n , Ed , Yol. 4, Interscience Publishers. I n c , S e w York, S . Y ,
1962.
(21) H . S. Harned and \\'. J . H a m e r , J . A m . Chem. Soc., 5 5 , 2194 (1933)
( 2 2 ) H S Harned and F. C . Hickey, O . P . , i b i d . , 6 9 , 2303 (1937).
( 2 3 ) A C Batchelder and C. L. A . Schmidt, J P h y s . Chem., 4 4 , 893
(1940).
Vol. 86
same type of behavior. The isotope effects in deu-
terated waterI5 can also be rationalized by either path,
since the effect observed is of the order of the de-
crease in ionization constants of both D20z4s25 and
weak acids in Dz0.z6
However, a serious objection to the hydroxide ion
attack is that the rate constant for the reaction would
have to be very large. Thus, if the rate-determining
step were
ki
I1 + OH- + products (8)
the rate expression would be
rate = kl[II][OH-] = kl(KzK,/ [H+][Cl-j) (9)
Substituting the value of K S estimated above and
the value of Kw and equating to the experimental
rate constant we get
M ) ( ~ OW)
-~-~ 2 X M2 sec.-l
(10)
" [H+][Cl-] [H + 1 [Cl- 1
Thus, kl would have a value of ca. 1013 1 k - l sec.-I
which is about lo4 larger than the rate for a diffusion-
controlled process in solution.27 The rate constant
for the route involving the hydroxo complex would be
much lower since the acidity of water is increased by
a factor of lo7to 10'O by complexing.20
The large intrinsic activity of water in nonaqueous
mediaz8 also favors the hydroxo species. This re-
activity, which is inconsistent with comparable nucleo-
philicities of water and acetate ion, however, is con-
water if the reaction proceeds by eq. 7 .
The hydroxo complex 111 can decompose directly
to product or proceed through another intermediate
such as a u-bonded complex. The isotope effect with
deuterated ethylene favors the u-bonded path. Since
tracer experiments? have shown that all four hydrogens
in the acetaldehyde come from the ethylene, if I11 de-
composes directly to product, the activated complex
would involve a hydride shift and a primary deuterium
isotope effect would be expected. The small isotope
effect actually observed argues against such a mech-
anism. The result would be consistent with the re-
actions represented by eq. 11 and 12 where the forma-
tion of the u-complex IV is rate determining. X small
k?
I11 +C1-Pd-CH2-CHz-OH
slow
+ C1- (11)
IV
fast
Cl-Pd-CH2-CHz-OH +HCl + Pd' + CHsCHO (12)
IV
isotope effect would be expected for kz since no C-H
bonds are broken.
(24) W F. K . Wynne-Jones, T r a n s . Favaday Soc., 32, 1397 (1936).
(25) T h e assumption ( r e f , 15) t h a t t h e reaction cannot go b y hydroxide
ion a t t a c k since t h e isotope effect found (4.05) does not correspond exactly
with t h e isotope effect on t h e K, of water (5.08) found by Wynne-Jones does
not seem justified since t h e difference could easily result from secondary
isotope effects
(26) C . K . Rule and \'. K . La M e r , J. A m . Chem. SOL.,6 0 , 1974 (1938).
(27) A. A. Frost and R. G. Pearson, "Kinetics a n d Mechanism," 2nd E d . ,
John U'iley and Sons, I n c . , S e w York, N. Y , 1961, Chapter 11.
(28) E . W. Stern, Proc. Chem. SOL., 111 ( 1 9 6 3 ) .
4ug. 20, 1964 OXIDATIOKOF ETHYLENE
BY AQUEOUS 11) CHLORIDE
PALLADIUM(
The intermediate IV is similar to those proposed for
the oxidation of ethylene by t h a l l i ~ m ( I I I ) . ~In the
case of this metal ion, it is postulated that the metal
leaves with its electrons to form a carbonium ion which
rearranges to give acetaldehyde or reacts with the sol-
vent to give ethylene glycol. (Treatment of /3-hy-
droxyethylamine in aqueous solution with nitrous
acid to yield this carbonium ion gives a mixture of
acetaldehyde and ethylene However, de-
composition of IV must not involve a carbonium ion,
since no glycol is found. The activated complex V,
in which palladium is assisting a hydride shift as it
leaves with its electrons, would fulfill these require-
ments.
V United States Industrial Chemicals. All other chemicals were
The chemical evidence appears to be compatible with
the u-bonded route. Palladous chloride seems capable
of adding across olefinic double bonds to form p-
oxyalkyl palladous chlorides.30 Furthermore, the
heavier group VI11 metals appear capable of labilizing
P-hydrogens. Platinum-ethyl compounds reversibly
eliminate ethylene to give platinum hydride.31 The
instability of palladium alkyls with /3-hydrogens3*
is probably due to the same type of reaction, the equi-
librium being driven to the side of decomposition
products by the instability of palladium hydride.3 3
One question which arises is the stereochemistry of
the reactive hydroxo complex 111. For rearrangement
to IV, a cis arrangement of the hydroxo and ethylene
would appear necessary while the trans effect of the
ethylene group would lead to a trans arrangementz0
However, even with the corresponding platinum com-
plex of 11, where the trans effect is stronger, there is
evidence that as much as 10% of the complex is present
as the cis isomer.34 Thus, in the case of I1 or I11 i t
is quite reasonable that kinetically significant amounts
of the cis isomer are present.
Assuming a reasonable value of for the value of
KBin eq. 6, we can estimate the value of kz in eq. 10.
Thus since
KZK3 - 2 x 10-4
rate = kz I11 = kz (14)
[H+][Cl-] [H+][Cl-]
we can calculate a value of ca. lo5 set.-' for kz if we
use a value of for K z . This value, although large,
is within a reasonable range.
The formation of vinyl esters in acetic a ~ i d ~
could well proceed by a similar route. Here, OH is
(29) H. C . Dehm, Hercules Powder Co., Bacchus, U t a h , unpublished
work.
(30) J. C h a t t , L . M . Vallarino, and L. M . Venanzi, J. Chem. Soc., 3413
(1957).
(31) J C h a t t and B L . S h a w . ibid., 5075 (1962).
(32) G. Calvin and G. E . Coates, ibid , 2008 (1960).
(33) J C h a t t , L A. Duncanson, and B. L Shaw, Chem. I n d . (London),
859 (1958).
(34) S. J . Lokken a n d D . S. M a r t i n , J r . , I n o r g . Chem., 2, 562 (1963).
(35) I . I . Moiseev, M . N. Vargaftik, and Ya K . Sirkin, Dokl. A k a d . N a u k
S S S R , l S S , 377 (1960).
( 3 6 ) E . W. Stern and M. L. Spector, Proc. Chem. Soc., 370 (1961).
3249
replaced by acetate in the activated complex V,
and a rapid rearrangement to a carbonyl compound is
impossible. Since 1,l-diacetates are not formed, the
preferred route would have to be the elimination of
proton along with the palladium. This proton could
leave as palladium hydride, or the acetate on the 6-
carbon may assist in its removal.
The lack of an acid inhibition for the oxidation of
cyclohexene to cyclohexanone is difficult to explain
on the basis of this mechanism unless T-complex for-
mation (eq. 5 ) is rate determining. It is also possible
that the oxidation is of the allylic type, giving cyclo-
hexenol, which rearranges to cyclohexanone in the
presence of palladous chloride. Cyclohexene appears
to have a tendency to undergo allylic oxidations with
metal ions6
Experimental
Materials.-The palladous chloride dihydrate was Fisher
Scientific Co. purified grade. The ethylene was purchased from
reagent grade.
Kinetic Runs.-The rate was measured by ethylene uptake.
Creased Flask.-The slower reactions, in which the ethylene
uptake was too slow t o be mass-transfer controlled, were run in
creased flasks a t a constant ethylene pressure of 1 a t m . T h e
gas uptake was measured by means of gas burets thermostated
a t the reaction temperature. T h e reaction flask was a 250-ml.
filter flask from which the side arm was removed and the opening
sealed. The side of the flask was indented to increase stirring
efficiency. A magnetic stirring bar was used for agitation.
In a typical run, the flask containing 50 ml. of the reaction
mixture was placed in a constant temperature bath and con-
nected to the gas buret by means of a large gage needle in-
serted through a rubber stopper in the mouth of the flask. The
system was then evacuated for several minutes with the stirrer
running. The stirring was then turned off and the system pres-
sured t o approximately 1 a t m . with ethylene. The mercury
in the gas buret and leveling bulb were then equalized, a reading
taken, and the stirrer turned on t o start the run. T h e pressure
was kept constant during the run by continuously leveling the
mercury in the gas buret and bulb.
In all runs except those showing C1- retardation, a plot of log
( Vm - V ) vs. time gave a straight line. The value of Vm was
calculated from the solubility of ethylene in the reaction mixture
plus the known concentration of the palladium chloride stock
solution, which was analyzed by the dimethylglyoxime method,
In the slower reactions, it was necessary to correct the value of
V for a slow side reaction, independent of palladous ion, which
consumed ethylene a t a slow b u t constant rate. The rate of
this reaction, which was probably hydration to ethanol, was de-
termined by measuring the rate of ethylene uptake for several
hours after the oxidation was completed. Solubilities were de-
termined by measuring the ethylene uptake solutions of the same
composition as the reaction mixtures but from which the pal-
ladous ion was omitted. Since the concentration of palladous ion
was small (-0.02 M ) compared to the total salt concentration
( 2 M ) ,its absence would not effect the solubility.
High-speed Reactor.-The high-speed reactor used for the
faster runs consisted of a 500-ml. jacketed glass container into
which were placed plastic baffles. The reaction mixture was
stirred b y a six-bladed turbine stirrer inserted into the reactor
~through
b ~ ~a mechanical seal. The stirrer was coated with Penton3'
t o prevent attack of palladous ion on the metal stirrer. Stirring
speeds were about 3000 r.p.m. This reactor was designed by
the Chemical Engineering Division of the Hercules Research
Center. 38
The procedure for making a run was identical with t h a t for
the creased flask runs except t h a t 250 ml. of the reaction mix-
ture was used. T h e plots of log ( V , - V ) v s . time deviated from
linearity after several minutes. This resulted from the release
(37) Hercules Powder Co. registered t-rademark for chlorinated polyether
(38) T h e author is indebted t o Dr V Verplanck and J J Hoglen for t h e
loan of t h e reactor, as well as for many suggestions regarding its use during
t h e course of this work
3250 N. C. BAENZICER
A N D J. J. HECENBARTH
of chloride ion as the reaction proceeded, four chlorides being
released per palladous ion reaction. Two runs were made in
the presence of finely divided palladium metal. T h e rate was
unaffected.
The following form was assumed in calculating the equilibrium
constant K
K = [(PdCl,C2H,)-] [Cl-] ' [PcICI~-~]
[C,H,]
T h e net ethylene uptake was converted t o moles of complex
and this subtracted from the total palladous ion concentration
to give [PdC14-2]. T h e value of [Cl-] was theti equal to total
chloride - 3 [( PdCI&HI) -1 - 4 [ PdC14-2] .
Constant Volume Reactor.-The constant volurne reactor was
essentially a 250-ml. florence flask connected to a mercury capil-
lary manometer. T h e flask was creased to increase the stirring
efficiency of the magnetic stirring bar. An outlet equipped with
stopcock was used t o transfer gas into the apparatus or t o pull
a vacuum. The volume of the reactor was found to be 253.8
ml. by nieasuring the pressure before and after the injection of a
weighed amount of mercury.
T h e reactions were run a t a n ethylene pressure of about 70
rnm. Since a t this pressure the concentration of complex is
small, eq. 2 can be written
[COSTRIBUTION FROM THE DEPARTMENT
O F CHEMISTRY, STATE
Crystal Structure of Diammonium Croconate and Molecular Orbital Calculations on the
Croconate Ion
BY N. c. BAENZICER
AND J. J . HECENBARTH
RECEIVEDJANUARY 11, 1964
The crystal structure of ( SH4)pCjOjwas determined, arid the molecular geometry of the croconate ion is re-
ported. Molecular orbital calculations were carried out to check the effect of the parameters h and k on the
calculated bond orders, electron densities, and delocalization energies i-alues of the parameters ~vvhicligive
the best agreement with the experimental bond orders and prescribed electron densities are reported.
Recent interest in a series of aromatic ions of general
formula C,O,-* has sparked renewed interest in the
structure of the croconate ion. A normal coordinate
analysis of the infrared and Raman spectral data of
the croconate ion indicates an anion of ~yrnrnetry.~
The structure of (NH4)2C606was undertaken to de-
termine the molecular geometry (bond distances,
bond angles) of the croconate ion. A preliminary ac-
count of the structure was reported.4
Bond orders, electron densities, and delxalization
energies (obtained from Huckel molecular orbital
(HMO) calculations) have been reported for a whole
series of oxygenated anions. The parameters used in
these calculations were h = 1.0 and k = 0.8.s
The molecular orbital calculations reported in this
paper were carried out to test the dependence of the
calculated bond orders, bond lengths, and delocali-
zation energies on the parameters h and k. I t was
hoped that a set of h and k could be found that would
give the observed bond orders, reasonable electron
densities,fiand a maximum delocalization energy. The
(1) R West, H Y . Xiu, D. I< Powell, and 51 D. E v a n s , J A m Chem
s o GSa,
I 6204 (1960).
( 2 ) R . West and H. Y . Niu, rbid , 84, 1321 (1962)
( 3 ) M I t o and R . West, ibid , 85, 2580 (1963).
( 4 ) N . C Baenziger, J. J Hegenbarth, and D. G. Williams, i b i d , 85, I538
(1963).
(A) R . \\'est and D L Powell. ibid , 86, 2577 (1963).
Yol. S(i
where
k'K
[Pd+2]= [I] + [PdC14-2]and k2 =
[Cl - 1 2 [H i
~
j
The solution of this equation for a conTtant voluriic re;tctor is
log
(a + P)f'[Pd+21
p i E q i j o - - <[($ j + j ~ i-iij
+ = kzt
where a is the Henry's law constant, [Pd+2Iois the initial pal-
ladous ion concentration, and @ is an instrument constant?Y
whose value is 8.5 X 1 0 - 5 for this reactor when 100 mi. ( ~ fsolu-
tion is used. The plots of the log term u s . 1 for all runs were
linear, indicating the reaction is first order in palladous ion and
first order in ethylene.
Acknowledgment.---The author gratefully acknowl-
edges helpful discussions with Dr. H . G. Tennent and
Professors 11. Kilpatrick, S.%%stein, and H. Taube.
The author also acknowledges the assistance of l l r .
John Jackson with experimental work.
(39) P Brandt and 0 Plum, Acta C h r m Scanil , 7 , 97 (19.53)
cXIVERSITY OF IOWA,IOWA CITY, IOIVA]
effect of including the overlap parameters in the cal-
culation was also investigated.
Experimental
The Crystal Structure of Ammonium Croconate .-( SHl)?C;Oi
crystallizes from aqueous solution as monoclini: needles or laths
with unit cell dimensions a = 7.444 f 0.003 A , , b = 13.345 =t
0.002 A . , c = 3.582 f 0.001 A . , = 99.4 i 0.3", Dmrnsci = 1.66
g . / c ~ n (pycnornetrically),
.~ Z = 2 , D x = 1.60 g./cm.3. The cell
constants were determined by a least-squares fitting of the (/io/),
( h k O ) , and (OkI) Weissenberg back-reflection data with extrapo-
lation to B = 90". The systematic absences, ( h k l ) when h k = +
2n + 1, indicate space groups C2/m, C2, or Cm. Space group
C2/m, which requires the croconate ion to have a symmetry cen-
ter, seemed unlikely from previous information.
T h e intensity data were taken using crystals (approximate
cylinders) maintained a t 8U"K. by use of a gas-flow dewar de-
signed in our laboratory.' The data were taken using the equi-
inclination Weissenberg camera, multiple film technique, and
Cu K a radiation ( A 1.5418 &k). Some diffraction spots a t high
angles were split into two spots due to thermal shock damage t o
the crystal. The amount of splitting varied from crystal t o
crystal, but the crystals used to take the intensity data showed
little effect of the splitting. The splitting was observed only
when the crystal was aligned along the needle ( c ) axis.
tions: qc = 3E,";'12(E0P + &P); -
(6) Reasonable electron densities were determined by using t h e e q u a ~
qo = ,3EoDj12(E,P E o P ) ; E,P and E,P
are Pauling's electronegativity numbers for carbon and oxygen. With the
use of the above eiluations, qc is calculated t o he 1 0. q,, t o be 1 . 4
(7) G. F. Richards Thesis, Feh , 1!464,