Metallo-boranes: A class of unconventional superhalogens defying electron counting rules

Superhalogens are a class of highly electronegative atomic clusters whose electron affinities exceed those of halogens. Due to their potential for promoting unusual reactions and role as weakly coordinating anions...

Synthetic, Spectroscopic, Structural, and Electrochemical Investigations of Ferricenium Derivatives with Weakly Coordinating Anions: Ion Pairing, Substituent, and Solvent Effects

A facile and effective strategy for the preparation of a series of ferricenium complexes bearing either electron-donating or electron-withdrawing substituents with weakly coordinating anions such as [B(C6F5)4]– or SbF6– is...

Super-electrophiles of Tri- and Tetra-Anions Stabilized by Selected Terminal Groups and Their Role in Binding Noble Gas atoms

Stabilization of multiply-charged atomic clusters in the gas phase has been a topic of great interest not only because of their potential applications as weakly-coordinating anions, but also for their...

Extending the chemistry of weakly basic ligands: solvates of Ag+ and Cu+ stabilized by [Al{OC(CF3)3}4]− anion as model examples in the screening for useful weakly-interacting solvents

Weakly Coordinating Anions (WCAs) facilitate formation of exotic “naked” cationic species. However, feasibility of the respective synthetic approaches may be limited by the basicity of solvent utilized, as the latter...

C–H Functionalization Reactions of Phenyl and Vinyl Carbocations Paired with Weakly Coordinating Anions

Carbocations have played a central role in the chemical sciences for over a century. In a synthetic setting, most methods utilize stabilized tricoordinate carbocations, while there are far fewer examples of reactions featuring nonstabilized dicoordinate cations. Here, we provide an overview of recent developments in the generation of high-energy carbocations mediated by weakly coordinating anions and the C–H insertion reactions of such carbocations. Moreover, we discuss mechanistic studies of these catalytic C–H insertion reactions aimed at furthering our understanding of the reactive nature of these rarely invoked cationic intermediates.1 Introduction2 Background: Phenyl Carbocations3 Silylium/Carborane-Catalyzed C–H Insertion Reactions of Phenyl Carbocations4 Silane-Fueled, Weakly Coordinating Anion-Catalyzed, Reductive C–H Insertion Reactions of Vinyl Carbocations5 C–H Insertion Reactivity of Vinyl Carbocations under Basic Conditions6 Conclusion and Outlook

Synthesis, structure and reactivity of NO+, NO˙ and NO− pincer PCN-Rh complexes

Synthesis of a rhodium PCN pincer-type nitrosyl complex is described. Coordination to the metallic center by weakly coordinating anions was found, as well as a slight stabilization of higher oxidation states when compared to a PCP analogue.

Two heads are better than one: improving magnetic relaxation in the dysprosium metallocene upon dimerization by use of an exceptionally weakly-coordinating anion

Combining two weakly-coordinating anions in the archetypical metallocene results in the first example of [BPh4]− as a bridging ligand in 4f metals, resulting in improved magnetic relaxation dynamics over its mononuclear counterpart.