J lnotg. Nucl. Chem., 1964, VoL 26, pp. 1157 to 1163. Pergamon Press Ltd.

Printed in Northern Ireland

THE THERMAL DECOMPOSITION OF METAL

COMPLEXES--XII
SOME COPPER(II) AMMINE COMPLEXES

J. P. SMITH and W. W. WENDLANDT

AFOSR Center for Molecular Research, Department of Chemistry,
Texas Technological College, Lubbock, Texas

(Received 2l October 1963; in revised form 16 December 1963)

Abstract--The thermal dissociation of [Cu(NHs)6]Br~, [Cu(NHs)6]CI2, [Cu(NHa)5]SO4, and

[Cu(NH~)4]Iz, was studied by differential thermal analysis, thermomagnetic analysis, pyrolysis on the
mass spectrometer, and by chemical analysis of the residues and reaction products. The complexes
dissociated through the loss of ammonia, forming stable lower ammines, and upon further heating,
the reduction of the copper(II) to copper(l) took place. The stoicheiometry of the thermal dis-
sociation reaction was determined.

THE thermal dissociation of the copper(II) ammine complexes has been the subject
o f a n u m b e r o f investigations. BLITZ et HI. (~) and EPHRIAM¢2'3) showed that the
[Cu(NHs)6]X 2 (X = C1, Br and I) complexes formed the pentammine-intermediates,
[Cu(NH3)5]Xz, on heating to moderate temperatures, and that at still higher tem-
peratures, the 3CuX2-10NH 3 complexes were formed. The latter complexes then
decomposed to give the diammine-complexes, [Cu(NH3)2]X 2. Although the tetram-
mine-complexes, [Cu(NHs)4]X 2, can be prepared, they were not observed as inter-
mediates during the thermal dissociation o f the hexammine-complexes. However, the
complex, [Cu(NHs)5]SO 4, was shown to form the [Cu(NH3)4]SO4, [Cu(NH3)2]SO4, and
[Cu(NH3)]SO 4 intermediates on pyrolysis (3). The latter complex, [Cu(NH3)]SO4,
darkened in colour and evolved a m m o n i a above a temperature of 360°C.
Earlier workers 14,5) have reported that the c o p p e r ( l l ) a m m i n e chlorides and bro-
mides produced a m m o n i u m halide and formed copper(l) halides upon heating to
elevated temperatures. A more recent investigation 16) has shown that the [Cu(NHa)2]X 2
(X -- C1 and Br) complexes formed a monoammine-complex, [Cu(NH3)]X2, which
then decomposed, giving the a m m o n i u m halide and Cu(l) halide. ANOUS(v) noted
that [Cu(NH3)2]SO 4 decomposed with the sublimation of (NH4)2SO 4 and the gradual
formation o f a dark-grey to brown coloured product.
The above thermal dissociation reactions appear to be similar to the thermal
dissociation of the cobalt (III) a m m i n e complexes which this laboratory has recently
investigated. (s-l°) It was found that the hexamminecobalt (III) halides and the
(1~ W . BLITZ, H . BROHAN a n d W . WEIN, Z. Anor~. Chem. 148, 207 (1925).
~2~F. Er'HRIAM,Ber. Chem. Dtsch. Ges. 52, 940 (1913).
¢u~F. EPHRIAM,Z. Physik. Chem. 83, 196 (1913).
(~ T. W. RICHARDSand H. G. SHAW,Amer. Chem. J. 15, 642 (1893).
('~)R. KANE,Ann. Cbim. Phys. [2], 72, 225 (1839).
('~)G. G. URAZOV,A. K. K1RAKOSYANand V. D. GALVSTYAN,Zh. Neor(. Khim. 2, 1094 (1957).
~7) M. M. T. ANOUS,Rec. Tray. Chem. 78, 97 (1959).
~s~W. W. WENOLANDT,J. lnor¢. Nuel. Chem. 25, 545 (1963).
~"~W. W. WENDLANDTand J. P. SMITH,J. Inor~. Nucl. Chem. 25, 843 (1963).
¢")) W. W. WENDLANDTand J. P. SMITH,J. Inor7. Nucl. Chem. 25, 1267 (1963).
1157
1158 J . P . SMIxn and W. W. WENDLANDT

halopentamminecobalt(III) halides thermally decomposed with the concomitant

reduction of the cobalt(III)ion to cobalt(II). If iodide ion was present in the complex,
it was the reducing agent for the reduction, forming elemental iodide as one of the
products. If no iodide ion were present, the coordinated ammonia was the reducing
agent, forming ammonium halide and nitrogen as the reduction products. The
complex, [Co(NHa)6]2(SO4)a, formed (NH4)2SO4, CoSOa, nitrogen and ammonia as
decomposition products during pyrolysis.
Little is known concerning the stoichiometry and thermal properties of the
reduction of Cu(II) ~ Cu(I) during the pyrolysis of the copper(II) ammine complexes.
It is thus the object of this investigation to study the deamination and the reduc-
tion reaction in the complexes, [Cu(NH3)6]X2 (X = C1, Br), [Cu(NH3)4]I2, and
[Cu(NHa)5]SO 4. The thermal dissociation reactions were studied by differential
thermal analysis, thermomagnetic analysis, pyrolytic techniques, and by chemical
analysis of the decomposition products.
EXPERIMENTAL
Preparation of metal complexes. The complexes,
[Cu(NHa)6]CIz, [Cu(NHs)6]Br~, and [Cu(NHs)5]SO,,
were prepared by exposing the anhydrous salts to ammonia gas until the proper weight levels were
attained. The complex, [Cu(NHa)4]I,'H,O, was prepared from an aqueous ammonia solution of KI
and CuCl2. ttl~ This compound was heated to 120°C in an ammonia atmosphere and then allowed
to stand for several days at room temperature in an ammonia filled desiccator until the proper weight
level was obtained. The complexes, [CuCNHa)~]Br~, [Cu(NHs)2]CI2, and [CufNHa)z]SO4, were pre-
pared by heatingthe higher ammines in a vacuum at 120-130°C for 12 hr. The complex, [Cu(NHa)2]I2,
was similarly prepared by heating the higher ammine for 3 hr at 75°C.
The higher ammine-complexes, [Cu(NI-Ia)6]X2, were very unstable; exposure to air for a short
time resulted in absorption of water and the evolution of ammonia. Unfortunately, there was some
exposure to air during the time required for loading the instrument samples.
The copper(II) ammine complexes were analysed for copper content by iodometric titration, and
for ammonia content by the Kjeldahl method. The results of the analyses are given in Table I.
TABLE 1.---ANALYTICAL DATA FOR COPPER(II) COMPLEXES

Cu (%) NH3 (%)

Compound Theoretical Found Theoretical Found

[Cu(NHa)6]CI~ 26"85 27"7 43'19 42'9

[Cu(NHs)6]Br~ 19"51 20"1 31 '36 31 '0
[Cu(NHs)4 ]I~ 16"48 16"3 17' 68 17"7
[Cu(NHs)~]SO4 25.96 25-9 34"80 34.9
[Cu(NHs)2]CI2 20"22 20-16
[Cu(NHs)2]Br2 13"23 13'00
[Cu(NHs)2]I~ 9"69 10"13
[Cu(NHs)2]SO4 17.60 17"38

Differential thermal analysis apparatus. This apparatus has previously been described. ~12~ Sample
sizes ranged in weight from 60 to 70 mg and were pyrolyzed in a dynamic helium or ammonia atmos-
phere at a furnace heating rate of 10°C per min.
High temperature Gouy magnetic balance. This apparatus has previously been described. ~1°~The
sample sizes ranged in weight from 60 to 70 mg, and were intimately mixed with an equivalent weight
~lt~j. B. BERTHEMOT, J. Pharm. 15, 445 (1830).
~2~ W. W. WENDLANDT,Anal. Chim. Acts 27, 309 (1962).
 The thermal decomposition of metal complexes--XII 1159

of dried AlzO3. The sample-Al~O8 mixtures were placed in evacuated, sealed Pyrex glass tubes, 3 mm
in diameter by 140 mm in length. A heating rate of l0°C per minute and a magnetic field of 8 kilogauss
were employed.
Mass spectrometric pyrolysis apparatus. This apparatus has previously been described. {13J From
3 to 10 mg of sample was pyrolyzed per run at a heating rate of 5°C per min. The various m/e peaks
of the pyrolysis products were scanned at periodic intervals during the pyrolysis. The following peak
intensities were plotted: for NH3, m/e ~ 16; for N2, 28; for H20, 18; and for SOs, 48.

®
\
©
LIJ
(.D
Z
<[
-1"
@
O
FIG. 1.--Thermomagnetic analysis
curves of the copper(II) ammine r-
complexes. T
£.9
A. [Cu(NH~)5]SO4
B. [Cu(NH3)6]CI2
C. [Cu(NH3)dBr~ __i
D. [Cu(NH3)4]I2 ta_l
cr

20 % II
k._
200 ' 3bo ' 4So '
TEMP., °C
Pyrolysis product analysis. The apparatus for the collection of the pyrolysis products consisted of
a Pyrex glass tube, 25 mm in diameter by 50 cm in length, one end of which was sealed off and fitted
with a small Nichrome wire-wound furnace. A removable cold-trap was attached on the other end of
the tube as well as a stopcock for aid in evacuation of the system. The temperature of the furnace
was measured by means of a chromel-alumel thermocouple located between the furnace windings
and the glass tube. The sample (200-300 mg) was weighed out into a tared porcelain boat, placed in
the furnace chamber, and the system evacuated to < 1 mm Hg for 15 min. The cold trap was then
cooled to liquid nitrogen temperature, and the furnace and sample chamber heated to 300°C at a
heating rate of 10°C per min. The ammonia, as well as the ammonium salts and the iodine, which
were evolved during the pyrolysis, were condensed in the cold trap. After the pyrolysis, the apparatus
was filled with dry helium. The ammonia was collected in a 4 % H~BO8 solution and titrated with
HC1; the ammonium halide and/or ammonium sulphate sublimates were removed from the system
by flushing with water and analysed gravimetrically for halide or sulphate ions; and the iodine was
collected in an aqueous solution of KI and titrated with a standard Na~S203 solution. The residue in
the boat was weighed and the amount of Cu(II) remaining was determined by an iodometric titration.
RESULTS AND DISCUSSION
Thermomagnetic analysis. The thermomagnetic analysis ( T M A ) curves of the
c o m p l e x e s are g i v e n in Fig. 1.
,3~ W. w . WENDLAND7and J. P. SMITH,J. Inorg. Nucl. Chem. In press.
1160 J.P. SMITHand W. W. WENDLANDT

The copper(II) ammine complexes are paramagnetic, due to a d 9 electron config-

uration for the Cu(II) ion, while the analogous Cu(I) compounds are diamagnetic,
having a d 1° configuration for the Cu(I) ion. Thus, it should be possible to follow the
reduction, Cu(II) -+ Cu(I), by noting the apparent weight decrease of the sample with
increasing temperature, on the Gouy magnetic balance. The reduction reaction in
[Cu(NHa)5]SO4, began at 380°C and took place in one step, terminating at 465°C. For

i
/
J I

. . . . . . . . . .
AT ,'4 f~- __."
®
V"
X I "--"

....... _-~°

/
® /

\ I /
"(~) •

,,,,./
5°C

i I I I i I I I I
I00 200 300 400
TEMP., °C.
FI~. 2.--Differential thermal analysis curves of the copper (II) ammine complexes in an
ammonia atmosphere (unless so indicated).
A. [Cu(NHs)6]Br~(helium atmosphere)
B. [Cu(NHs)6JBr~ F. [Cu(NHs),]I2
C. [Cu(NHs)z]Br2 G. [Cu(NHs)=]I~
D. [Cu(NHs)jCI2 H. [Cu(NH3).~]SO4
E. [Cu(NHs)z]CI2 I. [Cu(NH3)2]SO4
Dotted lines indicate the temperature range of the Cu(II) ~ Cu(I) reduction from TMA data (Fig. 1).
the other complexes, the reduction of [Cu(NHa)6]CI 2 started at 325°C; [Cu(NHa)6]Br 2
at 253°C; and [Cu(NHz)4]I2 at 208°C. Each change proceeded in what appeared to be
a single step. The order of stability towards reduction was the same as that found
for the hexamminecobalt (III) complexes, as far as the anion was concerned, or:
[Cu(NHz)~]I 2 (least stable) < [Cu(NHa)6]Br 2 < [Cu(NHa)6]C12 < [Cu(NH3)5]SO4~
An iodine sublimate was in evidence as the compound, [Cu(NHs)4]I e, began to change
weight on the magnetic balance.
Differential thermal analysis studies. The differential thermal analysis (DTA)
curves of the complexes are given in Fig. 2.
All of the DTA curves were characterized by a series of endothermic peaks caused
by the evolution of ammonia to lower ammine complexes and/or the reduction o f
the Cu(II) ion to Cu(1). In the presence of the ammonia furnace atmosphere, the
peak maxima temperatures were shifted 40-60°C higher than those found in the
 The thermal decomposition of metal complexes--Xll 1161

helium atmosphere studies. This can easily be seen in curves A and B of Fig. 2.
Curve A is the DTA curve for [Cu(NHa)6]Br 2 in a helium atmosphere while curve B
is the same compound pyrolyzed in an ammonia atmosphere. Similar results were
noted for the other complexes although the helium atmosphere curves are not
reproduced here.
The composition of the intermediate compounds was checked at various temper-
atures by weight change of the sample container. In this manner, the amount of
ammonia which was evolved from the initial compound could be determined.
Weight-loss of the samples up to 240-260°C, showed that except for [Cu(NH3)4]I 2
the higher ammine complexes had evolved ammonia to approach the composition for
the diammine-complexes, [Cu(NH3)2]X 2. At 250°C, [Cu(NH3)4]I a had evolved all of
its ammonia content and had undergone a reduction reaction to yield Cul. Weight-
loss data at still higher temperatures, 300°C, for [Cu(NH3)2]CI 2, showed that
[Cu(NH3)]C12 was formed while a monoammine-complex was also formed at 365°C
for [Cu(NHa)2]SO 4. No monoammine-complexes were found in the thermal dissocia-
tion of the complex, [Cu(NH3)2IBr2.
Since there was such a large dependence of the thermal dissociation peak maximum
temperatures on the surrounding furnace atmosphere, the magnetic data are best
compared to the ammonia atmosphere DTA curves because the T M A samples were
exposed to the ammonia evolved from the sample. The thermomagnetic reduction
temperature ranges are represented on Fig. 2 by the dotted lines.
The dissociation of the monoammine-, [Cu(NH3)]SO4, began in the DTA curve
at about 370°C, while the reduction reaction began at about 375°C. For the complex,
[Cu(NH3)2]Br2, the evolution of ammonia began at about 245°C, while the reduction
reaction began at about 250°C, and was completed at 355°C. The DTA curve for
[Cu(NH3)2]C1 e showed that the evolution of ammonia was almost completed before
the Cu(ll) ion reduction began. The DTA curve peak terminated at about 340°C,
while the reduction reaction began at about 330°C. The reduction of the Cu(II) ion
in the complex, [Cu(NH3)2]I2, began at about 200°C, while the evolution of ammonia
began at about 175°C.
Mass spectrometry studies. The gas evolution curves, as determined by the mass
spectrometer, for the decomposition products of the copper(II) ammine complexes
are given in Figs. 3 and 4.
The temperatures at which the reductions took place, as indicated by the nitrogen
evolution, were lower than those indicated by the TMA curves because the pyrolysis
was carried out in a vacuum. The temperatures at which nitrogen evolution began
were: [Cu(NHa)6]CI 2, 1750C; [Cu(NHa)6]Br2, 127°C; [Cu(NH3)4]I2, 77°C; and
[Cu(NH3)5]SO 4, 2500C. This latter complex also showed that SO~ and H20 were
evolved along with the nitrogen. The relative heights of the m/e -- 28 peaks for
[Cu(NH3)~]I 2 and [Cu(NH3)5]SO 4 were much lower than the nitrogen peak for the
complexes, [Cu(NHa)G]X. ., (X = C1, Br).
Product analysis studies: stoicheiometry of reaction. The results of the product
analyses of the complexes are given in Table 2.
The data agreed well with the following thermal dissociation reactions:
[Cu(NHa)~]X 2 --+ [Cu(NH3)2]X 2 + 4NH a (1)
6[Cu(NH3)2]X 2 ~- 6CuX + 6NH4X ~ N 2 " 4NH 3 (X == C1 or Br) (2)
 =
Oh

ml
REL. PEAK INT. REL. PEAK INT.
cn
..~ 0 ¸
C-
A .
I
n'1 z--r
o_
g

z
0

r.~
C-
A
z
3 ° =
T ~N
~. ~-Oo
tm
."o
~ d
~.. •

Q 0 Z

= =
ro
3
3 z
E
O
g
 The thermal decomposition of metal complexes--XII 1163

TABLE 2.--PRODUCT ANALYSIS OF COPPER(H) AMMINE COMPLEXES

NH4X/Cu I/Cu CuI/Cu II NH3/Cu*

Complex ratio ratio ratio ratio

[Cu(NH3)6]CI2 1-0 1.0 0.66

1.0"1" 1'0 0.67
[Cu(NHs)6]Br 2 0.9 1.0 0.67
1.0t 1.0 0.67
[Cu(NHs)a]I2 Trace 0"91 1.0 1.9
0~ 1.0 1-0 2-0
[Cu(NHs)5]SO4 0.4-0'5 0'6-0'7 0.8~-9

* Based upon Equation (2)

t Theoretical values

The amount of iodine formed by the pyrolysis of [Cu(NH3)4]I2 was 91 per cent
of the theoretical amount required for the reaction:
2[Cu(NH3)a]I 2 --~ 2[Cu(NHs)2]I2 --~ 2Cul + 12 -~- 4NH 3. (3)
The ammonia content was also low while the mass spectrometer indicated some
nitrogen evolution also. It seems then that the Cu(I1) ion in [Cu(NH3)4]I2 is reduced
by the iodide ion and ammonia, the former accounting for approximately 91 per cent
of the reduction, though different pyrolysis conditions may change this percentage.
The data for [Cu(NHs)5]SO ~ were too inconsistent to assign a definite reaction
stoicheiometry. It would appear that the formation of Cu2SO4, analogous to the
dissociation of [Cu(NH3)6]2(SO4)3, would be improbable as this compound is quite
unstable. It has been reported that an ammine complex of Cu2SO4 dissociates to
copper metal and cupric salts as low as 100°C. a4~
Here, as in the case of the cobalt(III) ammine complexes, that when iodide ion
is present, it is the primary reducing agent for the Cu(II) ~ Cu(l) reduction. If no
iodide ion is present, then ammonia is the reducing agent. However, unlike the
cobalt(II1) ammines, [Cu(NH3)5]SO4 was only slightly reduced and traces of sulphur
dioxide, water, and copper metal were in evidence.
It should also be noted that the reduction of the copper(lI) ion takes place at
the diammine- or monoammine-complex level and that higher ammines lose ammonia
by a reversible process to form these lower ammines which, upon further heating,
dissociate by an irreversible redox mechanism.
Acknowledgement--This work was supported by the U.S. Air Force Office of Scientific Research
through Contract No. AF-AFOSR-23-63.
~la~F. FORSTER and F. BLANKENBERG, Ber. Chem. Dtsch. Ges. 33, 3952 (1902).