A new CCC-NHC pincer ligand precursor architecture based on 1,3-bis­(N-alkylbenzimidazole)­benzene has been synthesized and metalated using Ag2O, forming a homobimetallic Ag complex with a metal to ligand ratio of 1:1. The Ag complex was treated with either [Rh­(COD)­Cl]2 or Rh­(COD)2OTf and NBu4I to yield a homobimetallic Rh complex by transmetalation. The Rh complexes were characterized, and an X-ray structure is reported. Their catalytic activity in the hydrosilylation of phenylacetylene is reported.

A report that demonstrated an efficient methodology for the arylation of imidazoles has been extended to bis(N-heterocyclic) compounds. Using bis(aryl) iodonium salts provides high-yielding access to CCC-NHC ligand precursors in a single step. Examples of arylation using various iodonium salts are reported herein with an investigation into the factors governing their relative rate of reactivity. The metalation of one of these compounds using Zr(NMe2)4 and its subsequent treatment with [Pt(COD)Cl2] to yield a transmetalated product are reported.

The coupling of N-heterocyclic azoles (imidazoles, benzimidazoles, triazoles) to bromobenzenes (1,2-; 1,3-; or 1,4) in a step-wise, sequential manner was accomplished by manipulation of reaction time and stoichiometry, which provided straightforward access to unsymmetrical bis(azolium) salts in only three isolation steps from commercially-available starting materials. Eight mono(azole) substituted bromobenzenes, four mono(azolium)bromobenzene salts, twelve unsymmetrical bis(azole)benzenes, and fourteen unsymmetrical bis(azolium) salts, which are precursors for pincer ligand complexes, are reported.

CCC‐NHC pincer ligands are prepared from bisimidazoles and bis(aryl)iodonium salts.