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The reaction of solid iron(II) phthalocyanine with hydrogen chloride gas
INORG.
NUCL.
CHEM.
LETTERS
Vol.
12,
pp.
1-5,
1976.
Pergamon
Press.
Printed
in
Great
Britain.
THE REACTION OF SOLID IRON(II) PHTHALOCYANINE WITH HYDROGEN CHLORIDE GAS by Larry L. Dickens and James C. Fanning Department of Chemistry and Geology Clemson University Clemson, South Carolina 29631 ~ece~ed 3 ~ 1 9 7 5 )
Concentrated hydrochloric acid reacts with iron(ll) phthalocyanine (Fe(II)Pc) in air to produce a solid of rather uncertain nature.
The
black crystalline solution product was originally reported to be iron(III) phthalocyanine chloride, CiFe(III)Pc
(1).
Later it was claimed to be an
iron(II) phthalocyanine hydrochloride, Fe(II)Pc'HC1
(2).
Recently, how-
ever, it has been described as a mixture of Fe(II)Pc, Fe(II)Pc'HC1, CiFe(III)Pc, and CIFe(III)Pc'HC1
(3).
In order to obtain a product of
more definite composition we reacted solid Fe(II)Pc with dry HC1 gas, eliminating any possible effects of water and air on the reaction. The gas-solid reaction was followed with a mass sorption or quartz spring balance and the weight changes determined as the Fe(II)Pc was exposed to HC1.
The solid sample, ca. 0.05 millimoles, was cooled to -78°C
in a dry nitrogen atmosphere.
Cold, dry HC1 was passed over the sample
and immediately the solid began to gain weight and increase in volume. The HC1 flow was continued for about ten minutes, the system closed and allowed to stand until no further weight change was observed. conditions
Under these
(-78°C and HC1 atmosphere), twenty moles of HCI per mole of
Fe(ll)Pc were added.
Dry nitrogen was passed over the sample at -78°C
and the HCI:Fe(II)Pc ratio decreased to 8:1.
Heating the latter adduct
2
Reaction of Solid lron(II) Phthalocyanine
Vol. 12, No. 1
to room temperature in a nitrogen atmosphere produced an adduct with four moles of HCI per mole of Fe(ll)Pc. The Fe(II)Pc-4HCI adduct was stable to HCI loss at room temperature and could be produced by the reaction of HCI gas with solid Fe(ll)Pc at room temperature.
Heating the adduct to 120-140°C removed three HCI's.
Stirring Fe(II)Pc'4HCI in aqueous 0.1M HN03 released three CI- ions as determined by titrating the filtered solution with 0.1M AgNO 3.
Dissolving
the adduct in dimethylsulfoxide, pyridine or o-dichlorobenzene produced a solution with the visible spectrum of Fe(ll)Pc. of the adduct at room temperature (3.69 B.M.).
The magnetic moment
(3.90 B.M.) is close to that of Fe(ll)Pc
The magnetic moment of the solution product is 3.3 B.M. at
room temperature
(4).
Table I - MSssbauer Spectral Parameters T,
Fe(II)Pc •4HCI
Fe(ll)Pc Solution Product
(Ref. i)
FePc "4HCI + water vapor
°K
6,
mm *
sec
A,
mm
sec
77
0.66
2.33
195
O. 61
2.31
295
0.56
2.33
77
0.72
2.66
77
0.54
2.56
77
0.52
2.53
•Values relative to Na2[Fe(CN)sNO].2H20. The M~ssbauer spectral parameters of Fe(II)Pc'4HCI were determined at 77 ° , 195 ° and 295°K (Table I).
Also included in Table I are the para-
meters for Fe(ll)Pc and the solution product.
The solution product was
prepared using the method of Barrett et al (i).
All three of the materials
gave sharp, two-line spectra which were relatively insensitive to temperature changes.
The parameters for Fe(ll)Pc and the solution product agree with
previously reported values
(5,6).
If Fe(II)Pc-4HCI is exposed to wet nitrogen gas and then dried; by weight change, three HCI's are lost. meters
of the solution product
The product has the MSssbauer para-
(Table I).
This product, as well as the
VoL 12, No. I
Reaction of Solid Iron(lI) Phthalocyanine
3
solution product, did not add HCI. Solid Fe(II)Pc acts as a basic material toward HCI gas, adding stoichiometric
amounts of HC1.
For Fe(II)Pc-4HC1,
HC1 molecules,
are weakly bound in the Fe(II)Pc lattice since they are
easily removed by either water or heat.
at least three of the
The addition of the four HC1 mole-
cules to Fe(II)Pc produces a small decrease in the ~ value and a larger decrease in 4.
These changes may be due to a reduction in the interaction
between neighboring Fe(II)Pc molecules.
This interaction has recently been
shown to play an important role in determing the ~6ssbauer parameters of Fe(II)Pc
(7).
No evidence for the oxidation of either iron(II) or the Pc ligand, forming the Pc(-l) w-cation radical, was observed in this study. pounds,
such as CIFe(II)Pc
~s-solid
reaction.
or Cl2Fe(lll)Pc(-l),were
Com-
not produced in the
Refluxing Fe(ll)Pc with conc. HCI in a nitrogen
atmosphere produces a dark green compound with a magnetic moment of 2.0 B.M. which may be CIFelIIPc
(3).
Heating FePc in nitrobenzene with thionyl
chloride produces CI2FelIIPc
(-i) which has a magnetic moment of 3.10 B.M.
and an isomer shift and quadrupole respectively
(3).
splitting of 0.35 and 2.15mm/sec,
The compound formed upon reacting Fe(II)Pc.4HCI with
water vapor appears to be Fe(II)Pc'Hcl. Experimental Fe(ll)Pc was purchased from Eastman Kodak, Rochester, Inc., Beverly, Mass.
N.Y. and Ventron,
The samples were purified by extracting with pyridine,
drying under vacuum, and triply subliming under high vacuum. Anal.
Calcd. for CeC32HI6N8: Found:
C, 67.62; H, 2.82; N, 19.72.
C, 67.86; H, 3.10; N, 19.82.
The HCI gas-solid reactions were carried out using a quartz spring balance Products
(8).
The spring, mounted in a glass tube, was a Worden Quartz
(Houston, Texas) Class D spring with a maximum load of 150 mg
and a ]mm/mg sensitivity.
The quartz pans weighed between 50-60 mg and
4
Reaction of Solid Iron(II) Phthalocyanine
contained about 25-30 mg of sample.
Vol. 12, No. 1
The HC1 entered the tube from the
bottom and a reaction temperature of -78°C was maintained with a dry ice-acetone bath. changes.
A cathetometer was employed to follow the weight
The balance was calibrated with Class M weights
(W. Ainsworth
& Sons) over the temperature range used for the weighings.
If 39 mg of
Fe(II)Pc were used, the addition of one HC1 per Fe(II)Pc produced a weight increase of 1.9 mg.
Weight changes of ± 0.1 mg were able to be observed.
High purity nitrogen was used for flushing the system.
Hydrogen chloride,
Matheson high purity grade, was passed through sulfuric acid before reacting with the solid samples.
The HC1 adduct prepared at -78°C was
heated under dry nitrogen on the balance to room temperature
and the
weight changes observed. A Cahn Model RG Electrobalance
and a microfurnace
controlled by a
Cahn Temperature Programmer were used to carry out the thermogravimetric analysis of FePc.4HC1 The
MGsshauer
in nitrogen.
spectra
(9) and the magnetic moments
(8) were determined
by previously described procedures.
Acknowledgement
- The authors would like to thank the Gulf Oil Corporation
for their support of this work and the Research Corporation for the funds used for purchasing the Mossbauer
spectrometer.
References
i.
P. A. BARRETT, D. A. FRYE, and R. P. LINSTEAD, J. Chem. Sot., 1157 (1938).
2.
J. c. JONES and M. V. TWIGG, J. Chem. Soc., A, 1546 (1970).
3.
J. F. MYERS, G. W. R. CANHAM, and A. B. P. LEVER, Inorg. Chem., 14, 461 (1975).
4.
A. B. P. LEVER, J. Chem. Soc., 1821 (1965).
5.
I. DEZSI, A. BALAZS, B. MOLNAR, V. D. GOROBCHENKO, and I. I. LUKASHEVICH, J. Inorg. Nucl., Chem., 31, 1661 (1969).
6.
A. HUDSON and H. F. WHITFIELD,
Inorg. Chem.,
6, i120 (1967).
Vol. 12, No. 1
Reaction of Solid Iron(II) Phthalocyanine
7.
T. R. SRIVASTAVA, J. L. PRZYBYLINSKI, and A. NATH, Inorg. Chem., 13, 1562 (1974).
8.
J. C. FANNING, C. D. ELROD, B. S. FRANKE, and J. D. MELNIK, J. Inorg. Nucl. Chem., 34, 139 (1972).
9.
J. C. FANNING, J. J. JEN, and A. J. MOUCHRT, J. Inorg. Nucl. Chem. (in press).
5
NUCL.
CHEM.
LETTERS
Vol.
12,
pp.
1-5,
1976.
Pergamon
Press.
Printed
in
Great
Britain.
THE REACTION OF SOLID IRON(II) PHTHALOCYANINE WITH HYDROGEN CHLORIDE GAS by Larry L. Dickens and James C. Fanning Department of Chemistry and Geology Clemson University Clemson, South Carolina 29631 ~ece~ed 3 ~ 1 9 7 5 )
Concentrated hydrochloric acid reacts with iron(ll) phthalocyanine (Fe(II)Pc) in air to produce a solid of rather uncertain nature.
The
black crystalline solution product was originally reported to be iron(III) phthalocyanine chloride, CiFe(III)Pc
(1).
Later it was claimed to be an
iron(II) phthalocyanine hydrochloride, Fe(II)Pc'HC1
(2).
Recently, how-
ever, it has been described as a mixture of Fe(II)Pc, Fe(II)Pc'HC1, CiFe(III)Pc, and CIFe(III)Pc'HC1
(3).
In order to obtain a product of
more definite composition we reacted solid Fe(II)Pc with dry HC1 gas, eliminating any possible effects of water and air on the reaction. The gas-solid reaction was followed with a mass sorption or quartz spring balance and the weight changes determined as the Fe(II)Pc was exposed to HC1.
The solid sample, ca. 0.05 millimoles, was cooled to -78°C
in a dry nitrogen atmosphere.
Cold, dry HC1 was passed over the sample
and immediately the solid began to gain weight and increase in volume. The HC1 flow was continued for about ten minutes, the system closed and allowed to stand until no further weight change was observed. conditions
Under these
(-78°C and HC1 atmosphere), twenty moles of HCI per mole of
Fe(ll)Pc were added.
Dry nitrogen was passed over the sample at -78°C
and the HCI:Fe(II)Pc ratio decreased to 8:1.
Heating the latter adduct
2
Reaction of Solid lron(II) Phthalocyanine
Vol. 12, No. 1
to room temperature in a nitrogen atmosphere produced an adduct with four moles of HCI per mole of Fe(ll)Pc. The Fe(II)Pc-4HCI adduct was stable to HCI loss at room temperature and could be produced by the reaction of HCI gas with solid Fe(ll)Pc at room temperature.
Heating the adduct to 120-140°C removed three HCI's.
Stirring Fe(II)Pc'4HCI in aqueous 0.1M HN03 released three CI- ions as determined by titrating the filtered solution with 0.1M AgNO 3.
Dissolving
the adduct in dimethylsulfoxide, pyridine or o-dichlorobenzene produced a solution with the visible spectrum of Fe(ll)Pc. of the adduct at room temperature (3.69 B.M.).
The magnetic moment
(3.90 B.M.) is close to that of Fe(ll)Pc
The magnetic moment of the solution product is 3.3 B.M. at
room temperature
(4).
Table I - MSssbauer Spectral Parameters T,
Fe(II)Pc •4HCI
Fe(ll)Pc Solution Product
(Ref. i)
FePc "4HCI + water vapor
°K
6,
mm *
sec
A,
mm
sec
77
0.66
2.33
195
O. 61
2.31
295
0.56
2.33
77
0.72
2.66
77
0.54
2.56
77
0.52
2.53
•Values relative to Na2[Fe(CN)sNO].2H20. The M~ssbauer spectral parameters of Fe(II)Pc'4HCI were determined at 77 ° , 195 ° and 295°K (Table I).
Also included in Table I are the para-
meters for Fe(ll)Pc and the solution product.
The solution product was
prepared using the method of Barrett et al (i).
All three of the materials
gave sharp, two-line spectra which were relatively insensitive to temperature changes.
The parameters for Fe(ll)Pc and the solution product agree with
previously reported values
(5,6).
If Fe(II)Pc-4HCI is exposed to wet nitrogen gas and then dried; by weight change, three HCI's are lost. meters
of the solution product
The product has the MSssbauer para-
(Table I).
This product, as well as the
VoL 12, No. I
Reaction of Solid Iron(lI) Phthalocyanine
3
solution product, did not add HCI. Solid Fe(II)Pc acts as a basic material toward HCI gas, adding stoichiometric
amounts of HC1.
For Fe(II)Pc-4HC1,
HC1 molecules,
are weakly bound in the Fe(II)Pc lattice since they are
easily removed by either water or heat.
at least three of the
The addition of the four HC1 mole-
cules to Fe(II)Pc produces a small decrease in the ~ value and a larger decrease in 4.
These changes may be due to a reduction in the interaction
between neighboring Fe(II)Pc molecules.
This interaction has recently been
shown to play an important role in determing the ~6ssbauer parameters of Fe(II)Pc
(7).
No evidence for the oxidation of either iron(II) or the Pc ligand, forming the Pc(-l) w-cation radical, was observed in this study. pounds,
such as CIFe(II)Pc
~s-solid
reaction.
or Cl2Fe(lll)Pc(-l),were
Com-
not produced in the
Refluxing Fe(ll)Pc with conc. HCI in a nitrogen
atmosphere produces a dark green compound with a magnetic moment of 2.0 B.M. which may be CIFelIIPc
(3).
Heating FePc in nitrobenzene with thionyl
chloride produces CI2FelIIPc
(-i) which has a magnetic moment of 3.10 B.M.
and an isomer shift and quadrupole respectively
(3).
splitting of 0.35 and 2.15mm/sec,
The compound formed upon reacting Fe(II)Pc.4HCI with
water vapor appears to be Fe(II)Pc'Hcl. Experimental Fe(ll)Pc was purchased from Eastman Kodak, Rochester, Inc., Beverly, Mass.
N.Y. and Ventron,
The samples were purified by extracting with pyridine,
drying under vacuum, and triply subliming under high vacuum. Anal.
Calcd. for CeC32HI6N8: Found:
C, 67.62; H, 2.82; N, 19.72.
C, 67.86; H, 3.10; N, 19.82.
The HCI gas-solid reactions were carried out using a quartz spring balance Products
(8).
The spring, mounted in a glass tube, was a Worden Quartz
(Houston, Texas) Class D spring with a maximum load of 150 mg
and a ]mm/mg sensitivity.
The quartz pans weighed between 50-60 mg and
4
Reaction of Solid Iron(II) Phthalocyanine
contained about 25-30 mg of sample.
Vol. 12, No. 1
The HC1 entered the tube from the
bottom and a reaction temperature of -78°C was maintained with a dry ice-acetone bath. changes.
A cathetometer was employed to follow the weight
The balance was calibrated with Class M weights
(W. Ainsworth
& Sons) over the temperature range used for the weighings.
If 39 mg of
Fe(II)Pc were used, the addition of one HC1 per Fe(II)Pc produced a weight increase of 1.9 mg.
Weight changes of ± 0.1 mg were able to be observed.
High purity nitrogen was used for flushing the system.
Hydrogen chloride,
Matheson high purity grade, was passed through sulfuric acid before reacting with the solid samples.
The HC1 adduct prepared at -78°C was
heated under dry nitrogen on the balance to room temperature
and the
weight changes observed. A Cahn Model RG Electrobalance
and a microfurnace
controlled by a
Cahn Temperature Programmer were used to carry out the thermogravimetric analysis of FePc.4HC1 The
MGsshauer
in nitrogen.
spectra
(9) and the magnetic moments
(8) were determined
by previously described procedures.
Acknowledgement
- The authors would like to thank the Gulf Oil Corporation
for their support of this work and the Research Corporation for the funds used for purchasing the Mossbauer
spectrometer.
References
i.
P. A. BARRETT, D. A. FRYE, and R. P. LINSTEAD, J. Chem. Sot., 1157 (1938).
2.
J. c. JONES and M. V. TWIGG, J. Chem. Soc., A, 1546 (1970).
3.
J. F. MYERS, G. W. R. CANHAM, and A. B. P. LEVER, Inorg. Chem., 14, 461 (1975).
4.
A. B. P. LEVER, J. Chem. Soc., 1821 (1965).
5.
I. DEZSI, A. BALAZS, B. MOLNAR, V. D. GOROBCHENKO, and I. I. LUKASHEVICH, J. Inorg. Nucl., Chem., 31, 1661 (1969).
6.
A. HUDSON and H. F. WHITFIELD,
Inorg. Chem.,
6, i120 (1967).
Vol. 12, No. 1
Reaction of Solid Iron(II) Phthalocyanine
7.
T. R. SRIVASTAVA, J. L. PRZYBYLINSKI, and A. NATH, Inorg. Chem., 13, 1562 (1974).
8.
J. C. FANNING, C. D. ELROD, B. S. FRANKE, and J. D. MELNIK, J. Inorg. Nucl. Chem., 34, 139 (1972).
9.
J. C. FANNING, J. J. JEN, and A. J. MOUCHRT, J. Inorg. Nucl. Chem. (in press).
5