An unusual reaction in nitromethane solution: use of the Cp*Rh moiety to form Prussian blue analogues

Abstract

The direct decomposition of nitromethane into nitrile compounds is a significant challenge due to the occurrence of severe side-reactions. In this study, we present a novel and gentle methodology for converting primary nitromethane into nitriles using [Cp*RhCl₂]₂. This reaction stands out for its simplicity and convenience under mild conditions. Moreover, the resulting nitrile serves as a direct precursor for the construction of organometallic complexes 1–3, through treating with different equivalents of AgOTf. Additionally, we conducted a systematic investigation into the mechanism of this reaction, revealing that the presence of AgOTf plays a crucial role in the formation of diverse organometallic cages. To provide comprehensive characterization, we employed various techniques including IR spectroscopy, ¹H NMR spectroscopy, HRESI-MS measurements, and single-crystal X-ray diffraction (SCXRD).