Infrared-Driven Charge Transfer in Transition Metal B12F12 Clusters

A combination of infrared multiple photon dissociation (IRMPD) spectroscopy and density functional theory calculations is used to investigate the structures and charge-transfer properties of clusters containing transition metals (TM = Co­(II), Ni­(II), Cu­(I), Zn­(II), Rh­(III), Pd­(II), Ag­(I), Cd­(II)) and the dodecafluorododecaboron dianion, B12F12 2–. In all cases, IRMPD resulted in transfer of electron density to the metal center and production of B12F12 –. Metals that exhibit the highest degree of charge transfer are found to induce reaction among the B12F12 cages, leading to production of B n F m (up to n = m = 24).