Establishing the NO oxidation state in complexes [Cl(5)(NO)M](n-), M = Ru or Ir, through experiments and DFT calculations |
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Authors: | Sieger Monika Sarkar Biprajit Zalis Stanislav Fiedler Jan Escola Natalia Doctorovich Fabio Olabe Jose A Kaim Wolfgang |
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Institution: | Institut fur Anorganische Chemie, Universitat Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany. |
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Abstract: | Predominantly NO-centered reduction was observed by EPR and IR spectroelectrochemistry to occur reversibly at low temperatures for Cl(5)Ir(NO)](-). In contrast, the Cl(5)Ru(NO)](2-) ion was found to undergo only irreversible reduction but reversible oxidation to a ruthenium(III) species at -40 degrees C. DFT calculations were used to establish the electronic structures and to rationalise the different stabilities. The calculations also reveal orientation-dependent energies and EPR properties between staggered and eclipsed conformations. |
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