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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.
2. Experimental section
2.1. Cis- and trans-dichlorobis(ethylenediamine) cobalt (III)
chloride
Co2+ + H+ + H2O2 → Co3+ + H2O Equation (1) Figure 1. Green solid trans-product
2CoCl2·6H2O + H2O2 + 2HCl (ac) + 4en → 2([Co(Cl)2(En)2]Cl + Sometimes, geometric isomers separation could be difficult
14 H2O Equation (2) [9]. In this work, in several tries, a mixture of cis and trans
product was obtained:
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-1M-1 (reported was 37 cm-1M-1
[12]). For cis-product the epsilon founded was 75,071 cm-1M-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 T2g→Eg 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 Δo, is low spin complex. Being a d6
In the last, the change from trans to cis was studied. The will have all its electrons paired in the t2g 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 px and py
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 px and pz
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 C2h, so by
taking its irreducible (Co-N) we obtain: Г= 3 Ag+2Bg+Au+3Bu
where Ag and
Bg are Raman active bands; Au and
Bu are IR active
bands. Also, the irreducible (Co-O) is: Г= Ag+Bu where
Ag is
Raman active band and Bu is the IR active band.
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.
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(TMPO). Spectroscopy Letters, 15(6), 423–433.
doi:10.1080/00387018208062667
12. Pineda Lanorio, Jocelyn; Gomez Lanorio, Jerry. Geometric
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6. Supplementary Material
Figure 14. Orbital molecular theory explaining the electron arrangement in peroxo and superoxo states.
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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.
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