NO+, NO•, NO-! Nitrosyl siblings from [IrCl5(NO)]-

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...

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Autores principales: Escola, N., Bikiel, D.E., Baggio, R., Di Salvo, F., Doctorovich, F.
Formato: JOUR
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Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00201693_v374_n1_p528_Escola
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Sumario: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 [IrCl 5(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. © 2011 Elsevier B.V. All rights reserved.