Low-temperature spectral observation of the first six-coordinate nitrosyl complexes of cobalt(II) meso-tetratolylporphyrin with trans nitrogen base ligands |
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Authors: | Kurtikyan Tigran S Markaryan Emil R Mardyukov Artur N Goodwin John A |
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Affiliation: | Molecule Structure Research Center NAS, 26 Azatutyan av, 375014 Yerevan, Armenia. |
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Abstract: | Low-temperature interaction of nitrogen base ligands with layered Co(TTP)(NO) (TTP = meso-tetratolylporphyrinato dianion) as well as its toluene solution leads to the formation of the first six-coordinate species of the general formula (B)Co(TTP)(NO) (where B = piperidine and pyridine). The nu(NO) stretching bands of these species appear at lower frequencies compared with the five-coordinate nitrosyl derivative and depend on the nature of the trans axial ligand. The equilibrium constants and enthalpies of formation of these new species are determined. Fairly stable at low-temperature conditions in the solid state, they slowly dissociate the nitrogen base ligands upon warming to restore the five-coordinate nitrosyl complex Co(TTP)(NO). |
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