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

• Published in: Inorganica Chimica Acta Vol. 374; no. 1; pp. 528 - 539
• Main Authors: Escola, Natalia, Bikiel, Damián E., Baggio, Ricardo, Di Salvo, Florencia, Doctorovich, Fabio
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.08.2011
• Subjects: HNO/NO; Iridium(III) complexes; Nitrosyl; Nitroxyl; NO[rad]; NO; Nitroxyl; HNO/NO; Nitrosyl; Iridium(III) complexes
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2011.02.063

Pentachloronitrosyliridate(III) ([IrCl5(NO)]−), the most electrophilic NO+ known to date, can be reduced chemically and/or electrochemically to produce the NO and HNO/NO− forms. The NO+ is practically linear but, its structural parameters are affected by counterions in the solid state. The other two nitrosyl redox states comprise bent structures. [Display omitted] ► The highly reactive pentachloronitrosyliridate(III) and related NO species. ► The whole NO family of [IrCl5(NO)]−: NO+, NO and HNO/NO−. ► The whole NO family forms of [IrCl5(NO)]−. ► [IrCl5(NO)]− and NO related species. 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.