Formation of thiolate-bridged diiron complexes featuring anionic isocyanide originating from the activation of counterions in the outer sphere

Abstract

Transition metal isocyanide complexes have attracted increasing attention owing to their versatile applications in catalytic organic transformations. Compared with metal complexes with neutral isocyanide ligands, those featuring anionic isocyanide groups are relatively rare and poorly understood. So far, there has been no report on structurally characterized metal anionic isocyanopentafluorophosphate complexes that may have potential for the development of some unique polymerization reactions. In this paper, we adopt a dicationic thiolate-bridged diiron complex as the reaction platform for the coordination activation and functionalization of cyanide. When treating with KCN, a facile salt metathesis with hexafluorophosphate anions occurred to generate monocyanide or dicyanide species. However, using trimethylsilyl cyanide as the substrate, an unsymmetrical diiron complex bearing a terminal [CNSiMe₃] ligand and an anionic [NCPF₅]⁻ group derived from the activation of one non-coordinating anion PF₆⁻ was obtained in a high yield. Interestingly, due to the lability of the N–Si bond in the [CNSiMe₃] ligand, it can play the role of an active site for the interaction with counter anions in the outer sphere. On one hand, this labile ligand can facilitate the activation of the P–F bond in PF₆⁻ and the C–B bond in BPh₄⁻ to afford structurally characterized thiolate-bridged diiron anionic isocyanopentafluorophosphate and isocyanotriphenylborate complexes, respectively. On the other hand, it can also interact with Lut·HCl to convert into a cyanide ligand stabilized by a hydrogen bonding interaction. This work represents a new synthetic pathway to furnish metal anionic isocyanide complexes.