Studies of Multicenter and Intermolecular Dihydrogen B–H···H–C Bonding in [4,8,8′‐<i>exo</i>‐{PPh₃Cu}‐4,8,8′‐(μ‐H)₃‐<i>commo</i>‐3,3′‐Co(1,2‐C₂B₉H₉)(1′,2′‐C₂B₉H₁₀)]

Abstract

Abstract An experimentally based and theoretical electron density study of the title compound has been carried out, giving the first experimental description for the two types of bonding: between the transition metal (i.e., Co) and the dicarbollide dianions that occurs through the open C 2 B 3 face of the nido ‐carborane and between the anionic commo cluster (i.e., Cobdc) and the transition metal (i.e., Cu) involving three unique (B–H) 3 ··· Cu bonds. The Co ··· dicarbollide and Cu ··· Cobdc bonds are shown to have a multicenter character, whereas direct Co ··· Cu interaction is found to be absent. The effect of the [Cu(PPH 3 )] + association with the Cobdc anion on the Co ··· dicarbollide bonding is discussed. The description of intramolecular Co ··· dicarbollide and intermolecular B–H ··· H–C connectivity in terms of the Hirshfeld approach and Voronoi tessellation is compared with the QTAIM results to confirm their qualitative and semiquantitative similarity.