NO, NO, NO! Nitrosyl siblings from [IrCl5(NO)] |
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Authors: | Natalia Escola Ricardo Baggio Fabio Doctorovich |
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Institution: | a Departamento de Química Inorgánica, Analítica, y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, INQUIMAE-CONICET, Ciudad Universitaria, Pabellón. 2, C1428EHA Buenos Aires, Argentina b Comisión Nacional de Energía Atómica, Avenida Gral Paz 1499, 1650 San Martín, Buenos Aires, Argentina |
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Abstract: | Pentachloronitrosyliridate(III) (IrCl5(NO)]−), the most electrophilic NO+ known to date, can be reduced chemically and/or electrochemically by one or two electrons to produce the NO and HNO/NO− forms. The nitroxyl complex can be formed either by hydride attack to the NO+ in organic solvent, or by decomposition of iridium-coordinated nitrosothiols in aqueous solutions, while NO is produced electrochemically or by reduction of IrCl5(NO)]− with H2O2. Both NO and HNO/NO− complexes are stable under certain conditions but tend to labilize the trans chloride and even the cis ones after long periods of time. As expected, the NO+ is practically linear, although the IrNO moiety is affected by the counterions due to dramatic changes in the solid state arrangement. The other two nitrosyl redox states comprise bent structures. |
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Keywords: | Nitrosyl Nitroxyl HNO/NO&minus NO els-cdn " target="_blank">com/sd/entities/rad" class="glyphImg"> Iridium(III) complexes |
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