Bimetallic Ru–Pd and Trimetallic Ru–Pd–Cu Assemblies on the Carborane Cluster Surface

Abstract

The synthesis of well-defined heterometallic complexes remains a frontier challenge in inorganic chemistry. We report an approach that relies on the sequential insertion of electrophilic metal fragments into electron-rich Ru–B bonds of the η2-BB-carboryne complex (POBBOP)­Ru­(CO)2 [POBBOP = 1,7-OP­(iPr)2-m-2,6-dehydrocarborane]. Utilizing this synthetic strategy, bimetallic (POBBOP)­(Ru)­(CO)2[Pd­(PtBu3)] and trimetallic (POBBOP)­(Ru)­(CO)2[Pd­(PtBu3)]­(CuBr) complexes were selectively prepared. Structural and theoretical analysis of the features of chemical bonding within Ru–B–B–Cu and Ru–B–B–Pd fragments is presented.

Ring-Expansion Reactivity of Ruthenium BB-Carboryne Metallacycle

“…The reactivity of the carboryne complex featured the metal−ligand cooperativity where one of the strained electron-rich metal− boron bonds of the BB>Ru fragment interacted with a range of electrophilic substrates, including protonation, halogenation, and insertion of Lewis acidic metal centers (Scheme 1). 60,62,63 In all cases, the strongly bound carbonyl ligands remained coordinated to the metal center.…”