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Synthesis and characterization of Dichlorobis(ethylenediamine) cobalt (III)


chloride and μ-Peroxo-bis(Pentaamminecobalt(III)) tetranitrate

Benavides G. D a​​ , Sanabria J. F. a​


a​
Departamento de Quimica, Facultad de Ciencias, Universidad Nacional de Colombia

ARTICLE INFO ABSTRACT

Article history: In order to improve the acquired skills in complex compounds and structural chemistry were
Elaborated: 18/07/2019 synthesized two structures: ​Dichlorobis(ethylenediamine) cobalt (III) chloride and
μ-Peroxo-bis(Pentaamminecobalt(III)) tetranitrate. In the first compound the geometrical isomers was
studied. ​The characterization of these two products was made with techniques as FT-IR, Raman,
magnetic susceptibility, elemental analysis and spectrophotometry. To explain each observation
and result, theories as crystal-field theory and molecular orbital theory were used. Cis and trans
Keywords: Complex, Inorganic synthesis, isomers from D ​ ichlorobis(ethylenediamine) cobalt (III) chloride were successfully obtained but
geometrical isomers, dioxygen binding. μ-Peroxo-bis(Pentaamminecobalt(III)) tetranitrate was not obtained. The explanation from these
results will be submitted using theories mentioned. There was evidenced the importance of
crystal-field theory and molecular orbital theory in the understanding of complex compounds.

2009 Elsevier Ltd. All rights reserved​.

1. Introduction Other big field in the modern chemistry is coordination


chemistry. Coordination chemistry is the study of coordination
Chemical synthesis is the core of modern chemistry. The main compounds or, as they are often defined, coordination complexes.
objective of this line of chemistry goes beyond simply finding These entities are distinguished by the involvement, in terms of
and synthesizing existing compounds in a natural way; Its simple bonding concepts, of one or more coordinate (or dative)
objective is to generate new materials according the growing covalent bonds, which differ from the traditional covalent bond
demand due to human activity. As per to recent reports, about 90 mainly in the way that we envisage they are formed [3]. These
million compounds have been developed or synthesized, coordination complexes have been relevant applications in
including natural and synthetic species, some of which have stereochemistry, catalysis, solid-state chemistry, supramolecular
become indispensable for our daily lives. These compounds have chemistry and nanotechnology, bioinorganic chemistry,
provided the basis for many scientific and technological advances metal-based pharmaceuticals, and even coordination polymer
in recent history. In turn, these advances have created (CP) [4].
increasingly urgent needs for new materials with specific
structures and functions, which poses challenges for This modern field in inorganic chemistry had a big develop in
understanding and scientific evolution. In modern times chemical the early 20​th century with the pioneering work of Alfred Werner.
synthesis is oriented towards "green chemistry", biomimetic He proved in 1911 the octahedral structure of [Co(en)​2​NH​3​X]​2+​, a
synthesis, inorganic synthesis under extreme conditions and metal containing six ligands [5]. Werner (Nobel prize in 1913)
molecular and structural engineering to produce inorganic obtained the first inorganic geometric isomer pair cis- and trans-
compounds efficiently, rationally and economically. These are, [Pt(NH​3​)​2​Cl​2​] and was the first in investigate the two geometrical
perhaps, some of the most essential elements for the continuous isomers that were synthetized in this experiment, cis- and trans-
and rapid advancement of science and technology in this era [1] dichlorobis(ethylenediamine) cobalt (III) chloride [6].
[2].
2
Other important structures as superoxo, μ-peroxo, and μ-oxo 3. Results and discussion
complexes are widely investigated. These Complexes with
dioxygen binding have several importance in nature. For 3.1. Cis- and trans- dichlorobis(ethylenediamine) cobalt
example, in copper and iron proteins these structures are used in (III) chloride
O​2​ transport and in substrates oxidation [7].
According the procedure, the first obtained product was a
Synthesis of cis- and trans- dichlorobis(ethylenediamine) green diamagnetic solid:
cobalt (III) chloride was developed. Also, the synthesis of a
μ-peroxo compound, the μ-Peroxo-bis(Pentaamminecobalt(III))
tetranitrate was explored. Their characterization using analytical
techniques as FTIR, Raman, elemental analysis,
spectrophotometry and magnetic susceptibility was performed

2. Experimental section
2.1. Cis- and trans-dichlorobis(ethylenediamine) cobalt (III)
chloride
Co​2+​ + H​+​ + H​2​O​2​ → Co​3+​ + H​2​O ​Equation (1) Figure 1​. Green solid trans-product

2CoCl​2​·6H​2​O + H​2​O​2 ​+ 2HCl (ac) + 4en → 2([Co(Cl)​2​(En)​2​]Cl + Sometimes, geometric isomers separation could be difficult
14 H​2​O Equation (2) [9]. In this work, in several tries, a mixture of cis and trans
product was obtained:

The synthesis of this products was adapted from Ayelabola ​et.


al ​[8]: Cobalt(II) chloride hexahydrate (3,024​±0,001​) g was
dissolved completely in distilled water (20​±1)​ mL. Anhydrous
ethylenediamine (1,032​±​0,001) g in (10​±1)​ mL of water was
then added. Hydrogen peroxide (20​±1)​ mL, 30% was added
dropwise with stirring. The oxidized solution was cooled in ice
and (10​±1)​ mL of concentrated HCl was added with stirring. A
dark ruby red solution was formed. The solution was then
concentrated in a water bath and cooled. Dark green crystals were
obtained. The crystals were thereafter dissolved in
methanol-diethyl ether 1:1 solution, filtered, and dried in an oven
at 100°C. Yield: (2,946​±0,001) ​g; 81,2%. The green Figure 2​. Mixture of cis- and trans-product
trans-dichlorobis(ethylenediamine)cobalt(III) chloride obtained
was then dissolved in a minimum amount of water, heated, and When a real soft heating of trans product was developed the
evaporated to dryness to give a glassy deep violet product. This apparent purity of cis product was improved:
was filtered and washed with iced cold water to obtain a violet
powder of cis-dichlorobis(ethylenediamine)cobalt(III) chloride.
2.2. μ-Peroxo-bis(Pentaamminecobalt(III)) tetranitrate
​2Co(NO​3​)​2​· 6H​2​O + 10 NH​3(ac)​ + O​2​ →
[{Co(NH​3​)​5​}​2​(μ-O​2​)](NO​3​)​4​ + 12 H​2​O
Equation (3)
6,6161g ±0,0001 of Co(II) nitrate hexahydrate was dissolved in
5,5mL ±0,1 of water and filtered. Aqueous ammonia (15M,
7,3mL ±0,1 ), and after the mixture has been cooled in ice bath, a
current of air is passed (2-3 hours) stirred with a magnetic stirrer
Figure 3.​ Violet and solid cis-product
at 0-5 ℃. In a 50 mL Erlenmeyer flask, the solution is placed and
air is bubbled with a glass dropper connected to a vacuum pump, According the species distribution diagram, the
always leaving the tip of the dropper inside the solution, and ethylenediamine added in the reaction medium must be
covering the Erlenmeyer flask with a stopper but without controlled seeking the formation of the bi, and not the mono or
adjusting it. all to allow air flow. Sodium nitrate (2,6464 tri-ethylenediamine.
±0,0001​) dissolved in 6,2 ​mL ±0,1 of water is the added; air is
passed through the solution for another hour, with the mixture
cooled with ice toward the end of this period. The dark brown
crystals are gathered on a filter paper and washed with small
quantity of 15 M of aqueous ammonia and then with ethanol.
3
Raman and B​1g​, B​2u and
​ B​3u are active bands in IR. While for cis
isomer 2A​1​, B​1​ and B​2 ​are both active bands in FT-IR and Raman.
Co-N stretching modes occurs around 510-600 cm​-1 ​[10].
Within this range it is possible to see in cis-spectrum (Figure 17
and 19, supplementary material) three IR signals according the
active bands mentioned. In Raman was possible to see just one
but wide band in 516 cm​-1​. It is possible than the two active bands
were overlapped.
For trans-isomer, two active signals were the expected for
Raman and three for IR spectrums. In this range, for IR it is not
clear the existence of a signal because the baseline is in low
transmittance. But in Raman it is clear the presence of two
overlap signals around 516 cm​-1 (Figure 18 and 20,
Figure 4​. Species distribution diagram for Co(III) ethylenediamine supplementary material).
complex compound. Blue is the free methal, orange the mono-denteded, gray
the bi-dentaded and yellow the tri-dentaded In FT-IR there was not possible to study Co-Cl bond because
this bond appears around 300cm​-1 [11]. But in Raman was
The molecular formula from dichlorobis(ethylenediamine) possible to see around this wavelength.
cobalt (III) chloride is C​4​H​16​N​4​Cl​3​Co. Table 1 show elemental
analysis obtained in comparison with theory: For Co-Cl bonds. The irreducible representations for cis- and
trans isomers are Г= A​1​+B​1 and Г= A​g​+B​1u​, respectively. The
Table 1​: Theoretical and obtained subtotal mass for cis- and
active bands in Raman for cis are A​1 and B​1 bands and for trans is
trans-product.
just A​g.
Element Theoretical Obtained Obtained In Raman spectrum of cis-isomer it is possible to see two
subtotal mass subtotal mass subtotal mass overlap signals around 282 cm​-1 and ​ for trans isomer just one
(%) Cis (%) Trans (%) intense signal around 270 cm​-1​ as expected.
The other observed signals are explained in the table 2:
C 16,83 13,0144 15,8520
Table 2: ​Explained signals for IR spectrum of cis- and trans-isomers
H 5,65 4,9021 5,2193
Bond Type v (cm​-1​)
N 19,62 15,2205 17,1765
N-H Stretch 3400
Cl 37,25 - -
C-H Stretch 3200
Co 20,64 - -
N-H Deformation 1600-1500
vibrations
In general, results show the same trends according theoretical
valours, giving and additional evidence about the compound that C-H Bend 1400
was synthetized.
C-N Bend 1000
The symmetry point group for cis is C​2​v and for trans is D​2​h.

By crystal field theory is obtained a low spin electronic


configuration because ethylenediamine ligand is a strong field
ligand (although chlorides are weak field ligands), so the d​6
Co(III) most be diamagnetic.
That was proved in magnetic susceptibility experiment: The
green solid obtain a magnetic susceptibility of -009, (X = J / Bo);
if X<0 opposes the external shield is diamagnetic. The magnetic
susceptibility for the violet solid was -008 (Also diamagnetic).
The octahedral crystal-field splitting for both Trans and cis
Figure 5​. Representation of trans and cis geometrical isomers.
isomer is submitted in the figure 6.

From irreducible representations there was obtained, for Co-N


bond, Г= A​g​+B​1g​+B​2u​+B​3u for trans isomer and Г= 2A​1​+B​1​+B2
for cis isomer. For trans isomer, A​g ​and B​1g are active bands in
4

Figure 6. ​Octahedral crystal-field splitting for low spin Co (III).

There was developed a Uv-vis spectrum from these products Figure 8​. Solid obtained with synthesis
(see figures 21 and 22, supplementary material). Maximum
The solid has a magnetic susceptibility of +075, the positive
wavelength for trans product was 618 nm, the same reported by
values of this property indicate that it is paramagnetic (X = J /
Pineda ​et al ​[12]​. For cis product the maximum wavelength was
Bo; if X<0 opposes the external shield is diamagnetic or X>0
508 nm (The reported was 509 nm).
when augments the external shield and been paramagnetic)​13
By standard addition method there was determined the epsilon what gave us one unpaired electron at the end.
for cis, and trans isomers (figures 23, 24) The epsilon constant
for trans product was 29,368 cm​-1​M​-1 (reported was 37 cm​-1​M​-1
[12]). For cis-product the epsilon founded was 75,071 cm​-1​M​-1​.
These low ε are for M→M transitions caused by crystal field
splitting. There are not M→L transitions because ligands have
not insaturations and methal is in a high oxidation state. Nor
L→M occurs because ligand have not a high electron density.
With this in mind, the M→M transition is spin-forbidden Figure 9. ​Structure of ​μ-Peroxo-bis(Pentaammincobalt(III)) tetranitrate (the
because when T​2g​→E​g ​transition occurs two pairing electrons end of each cobalt bond (5) ends in amine (NH3)). Co(III), 18e-​ .​
must be unpaired changing, thus, spin. Also, this transition is The μ-peroxo complex presents (5) ammin ligands that are strong
Laporte-forbidden for the low ε founded. field ligands so have a high Δ​o​, is low spin complex. Being a d​6
In the last, the change from trans to cis was studied. The will have all its electrons paired in the t​2g orbitals, this explains
isomer changing is explained by trans effect. A ‘trans-effect’ has why it is diamagnetic. But our product have one unpaired
been defined as ‘the effect of a coordinated group on the rate of electron (paramagnetic). This is explained if we see the Figure 14
substitution reactions of ligands trans to itself’, chloride ligand is in the supporting material [14], here the molecular orbital
one of the best trans-labilizers ligands [13]. The trans-cis diagram of superoxo show that while in the peroxo the p​x and p​y
isomerization was followed by spectrophotometric experiments antibonding orbitals of symmetry π are paired since they receive
and equilibrium diagram was elaborated: 2 electrons (one of each cobalt atom), the peroxo p​x and p​z
antibonding orbitals of symmetry π only one is paired and the
other unpaired, this unpaired electron is the one that gives the
property of paramagnetism to the complex.
The point group of the μ-peroxo complex(figure 9) is C​2​h, so by
taking its irreducible (Co-N) we obtain: Г= 3 A​g​+2B​g​+A​u​+3B​u
where A​g and
​ B​g are Raman active bands; A​u and
​ B​u are IR active
bands. Also, the irreducible (Co-O) is: Г= A​g​+B​u where
​ A​g is
Raman active band and B​u​ is the IR active band.

Figure 7​. Equilibrium diagram of Cis and trans-isomers.

3.2. μ-Peroxo-bis(Pentaammincobalt(III)) tetranitrate


Figure 10.​ Structure of dibridged superoxo complex.Co(III), 18e​-​.
With the results obtained, we believe that we did not get what
we expected. Below we will explain this assumption. Our product The μ-superoxo complex have point group C​2v​. so by taking its
should be dark brown and diamagnetic. What we got were irreducible (Co-N) we obtain: Г= 3A​1​+1A​2​+1B​1​+3B​2 where
brown-green-black (figure 1) and paramagnetic crystals. A​1​,A​2​,and B​2 are IR active bands; all are Raman active bands.
Also, the irreducible (Co-O) is: Г= A​1​+B​2 where all are active
bands in Raman and IR. The irreducible and actives band to
(Co-X) is the same of (Co-O).
The Raman spectrum (figure 12) presents the following bands:
5
Table 3: ​Explained signals for Raman spectrum of peroxo and superoxo Table 5​. Absorption maxima and νO-O (cm​-​¹) in different μ-peroxo and
μ-superoxo [15]​.
ν Reported ν Reported ν Finding Type of signal
(superoxo)​19 (peroxo)​19

-- -- 3113,62 stretching N-H

-- -- 1669,67 bending N-H


The product obtained was determined its wavelength maximum
-- -- 1385,29 Stretching N-O absorbance (figure 13, supporting material). Found that was 358
nm with shoulder in 676, when addressing table we observed
that the searched was 300 nm with shoulder in 430 nm but the
1075 800 1067,50 stretching O-O
one obtained is more similar to that reported for a dibridged
superoxo [15]. Through of a standard addition curve, several
1060 -- 1052,10 Stretching O-O points were calculated and its absorbance was taken (figure 15)
with this we can know the value of the epsilon when determining
762 642 723,98 Stretching Co-O its slope (349.55 cm​-1​M​-1​). This value of ε show that this
transition allowed by spin in non-centrosymmetric complexes
675 547 691,05 Stretching Co-O (~250 cm​-1​M​-1​). What continues confirming that we did not
obtain the μ-peroxo since this has an investment center. The
532 496 521,98 Stretching Co-N complex that we sustain find (μ-superoxo) instead has no
investment center. This band of maximum absorption, is a load
transfer band (reductive band) L➝M​16​, where the unpaired
459 -- 481,2 Stretching Co-N
electron of the superoxo passes to the empty orbitals of the metal
In this spectrum we can see the most marked coincidences with this the selection rule of being allowed by spin is fulfilled.
between the compound obtained and the μ-superoxo, but not with This band occurs when the metal is in a high state of oxidation
the μ-peroxo, among them we can see the band in 1067cm​-1 of the (Co (III)). Like the dichromate that also has this type of
O-O stretch of our compound while in ours the peroxo is in 830 transition, our product was very colored upon dissolution.
cm​-1​, also the appearance of another stretch Co-O referring to the The reasons why we did not obtain can be broad, the first is that
amido bridge in 459cm​-1​. the compound is only stable in 7M solutions of ammonia and
The IR spectrum (figure 11) presents the following bands: highly hygroscopic [16] . The compound is unstable to heat and
in the presence of water vapor [17]. And not knowing what
Table 4: ​Explained signals for IR spectrum of peroxo and superoxo happened, it was left in a "camera" with atmosphere of ammonia
(25%) water from the environment while we built the camera and
ν Reported ν Reported ν Founded Type of signal that this solution also contained water made the product become
(Superoxo) (peroxo) liquid, that is to say that its had decomposed. It was decided to
leave only covered for 7 days in the ammonia chamber, it never
-- -- 3426,06 stretching N-H returned to take solid aspect, so it was left only in desiccator and
at 4 hours a solid coffee-green-black was obtained. Another
-- -- 3200,71 stretching N-H reason, is that the reactor where it was carried out was not the
most indicated, when starting the pumping of air it was evident
2398,69 how much of the solution went to the walls, to the erlenmeyer
nozzle, and even to the hose the air pump which did not let it be a
homogenous environment where the peroxo was formed, but it
1765,11 was an environment where from time to time these droplets
would fall to the walls changing the concentrations of the initial
1628,83 bending N-H complex. Having less complex it oxidized faster. We also believe
that the concentration of ammonia which was in a range of tetra
-- -- 1384,21 Stretching N-O and penta coordination pNH​3 = 7.5 (see species diagram, figure),
and oxidation of the peroxo group, favored the arrangement of
832 828 831,45 Stretching O-O the amido group as a bridge ligand.

4. Conclusions
659,52
Cis and trans isomers from Dichlorobis(ethylenediamine)
474,94 Stretching Co-N cobalt (III) chloride were successfully obtained. The correlation
between theory and obtained results allow the right
For the IR spectra, almost no information was found, it is characterization from these products.
necessary to study more these dibridges and peroxo.
6
​ -Peroxo-bis(Pentaamminecobalt(III)) tetranitrate was not
μ Acid and Glycine. Bioinorganic Chemistry and Applications,
obtained. But we believe that the μ-amido-μ-superoxo 2017, 1–15. doi:10.1155/2017/2956145.
9. Poole, C. F. (2003). Separation of Stereoisomers. The Essence of
tetraamminecobalt (III) tetranitrate was obtained, as has been
Chromatography, 793–845.
supported in both IR, raman, uv-vis and magnetic susceptibility doi:10.1016/b978-044450198-1/50023-9
experiments. 10. Poon, C., K. ​The Infrared Spectra of Some Cis- and Trans-Isomers
of Octahedral Cobalt(III) Complexes with a Cyclic Quadridentate
Finally, there was evidenced the importance of crystal-field Secondary Amine​. 1970. Contribution of the department of
theory and molecular orbital theory in the understanding of chemistry. University of Hong Kong.
complex compounds allowing correctly characterization of this 11. Alves, O. L., & Hase, Y. (1982). ​The Infrared Spectra of
family of chemical substances. Cobalt(II) Halide Complexes with Trimethylphosphine Oxide
(TMPO). Spectroscopy Letters, 15(6), 423–433.
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12. Pineda Lanorio, Jocelyn; Gomez Lanorio, Jerry. ​Geometric
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Synthetic Chemistry, 189–217. 15. Hess F. Solid Oxide Fuel Cell Materials and Interfaces. 2018,
doi:10.1016/b978-0-444-63591-4.00008 Handbook of Materials Modeling. Vol 2 Applications: Current and
5. Bailar, J. C.; Jr., ​Research in the Stereochemistry of Cobalt Emerging Materials, Publisher: Springer, Cham, pp.1.
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Compounds, ​ACS symposium Series No. 119, Bodie E. Douglas ,u-Peroxo and p-Superoxo Cobalt (111) Amine Complexes from
and Saito Yoshihiko, Eds, American Chemical Society. Raman Spectroscopy.American Chemical Society. Inorganic
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7
6. Supplementary Material

Figure 11.​ IR spectrum of product in the “μ-peroxo” synthesis.

Figure 12. ​Raman spectrum of product in the “μ-peroxo” synthesis.


8

Figure 13. ​UV-VIS spectrum of the product in the μ-peroxo synthesis

Figure 14. ​Orbital molecular theory explaining the electron arrangement in peroxo and superoxo states.
9

Figure 15. ​Standard addition in μ-peroxo product.

Figure 16. ​Species distribution diagram for Co(III) amine complex compound. Black is the free methal, red the mono-coordinated, gray the bi-coordinated, dark
blue tri-coordinated, light blue tetra-coordinated, violet the penta-coordinated and yellow the hexa-coordinated complex.
10

Figure 17.​ IR spectrum of cis-isomer​.

Figure 18. ​IR spectrum of trans-isomer​.


11

Figure 19. ​Raman spectrum of cis-isomer.

Figure 20. ​Raman spectrum of trans-isomer.


12

Figure 21. ​Uv-Vis spectrum for trans.isomer.

Figure 22. ​Uv-Vis spectrum for cis-isomer.


13

Figure 23. ​Standard addition of trans product.

Figure 24. ​Standard addition of cis product.


14

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