The weakly coordinating anion [Me3 NB12 Cl11 ](-) has been prepared by a simple two-step procedure. The anion [Me3 NB12 Cl11 ](-) is easily obtained in batches of up to 20 g by chlorination of the known [H3 NB12 H11 ](-) anion with SbCl5 at about 190 °C and subsequent N-methylation with methyl iodide. Starting from Na[Me3 NB12 Cl11 ], several synthetically useful salts with reactive cations ([NO](+) , [Ph3 C](+) , and [(Et3 Si)2 H](+) ) were prepared. Full spectroscopic (NMR, IR, Raman, TGA, MS) characterization and single-crystal X-ray diffraction studies confirmed the identity and purity of the products. The thermal, chemical, and electrochemical stability as well as the basicity of the [Me3 NB12 Cl11 ](-) anion is similar to that of the structurally related weakly coordinating 1-carba-closo-dodecaborate and closo-dodecaborate anions. The facile preparation of the [Me3 NB12 Cl11 ](-) anion and its ideal chemical and physical properties make it a cheap alternative to other classes of weakly coordinating anions.

Silver(I) salts of weakly coordinating anions (WCA) are commonly applied as oxidizing agents or halide abstracting reagents. The feasibility of a particular silver salt for such applications strongly depends on the "nakedness" of the silver cation. In this study the reactivity of Ag[Me 3 NB 12 Cl 11 ] in different solvents was investigated. Crystal structures of a variety of complexes were obtained. In several crystal structures two boron clusters are bridged by Ag-Cl contacts.

The synthesis of salts of reactive cations and weakly coordinating anions is of great interest to the development of catalysts, because the weak electrostatic interaction between the two may greatly increase catalytic activity and solubility in nonpolar solvents. However, the synthesis of these salts is in many cases difficult and requires elaborate, sometimes multi‐step procedures. Here, we describe the synthesis of a library of monocationic group 11 metal‐triphenylphosphine complexes of dodecaborates generated by means of electrochemistry. The complexes of the general formula [M(PPh3)y(CH3CN)z]2[B12X12] (M=Cu, Ag, Au; X=H, F, Cl, Br, I; y=2–4; z=0–2) were synthesized from the free acid of the respective dodecaborate and the elemental metal in acetonitrile in the presence of triphenylphosphine. The reactions were performed in an electrochemical cell under ambient conditions in polypropylene containers in all cases. A total of 13 different crystal structures in the [M(PPh3)y(CH3CN)z]2[B12X12] system were obtained. As a by‐product in some reactions single crystals of [(H3O)(OPPh3)3]2[B12X12] (X=Cl, Br, I) were found.

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