Carboranes are attractive molecules that have been utilized in organometallic chemistry to study the metal-boron interactions in both coordination behavior and reactivity. Transition metal benzyne complexes, which exhibit η2-coordination with the metal, have been studied extensively in the activation of small molecules. Due to the unique geometry of the carborane cage, a metal can bind to the cluster via two neighboring boron atoms in an η2 fashion resulting in a BB-carboryne which is an inorganic analog of benzynes. In addition to the strong trans influence exerted by the BB-carboryne ligand, the Ru-B bonds that are electron rich and highly strained in the (BB)&gt;Ru metallacycle act as nucleophilic reaction centers in bond activation of small molecules exhibiting the metal-ligand cooperativity. The pincer ligand framework stabilizes the highly reactive Ru-B bonds in these carboryne complexes. Herein we have expanded the synthetic scope of auxiliary ligands in carborynes from strongly bound carbonyl groups to labile benzonitrile and diphenylphosphine ligands. The reactivity of these novel complexes in bond activation of small molecules and the synthesis of heterometallic complexes was studied, thus widening the broader applicability of (BB)-carboryne complexes in organometallic chemistry.

Synthesis and reactivity of novel Ru (BB)-carborynes

ACS Spring 2022

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