Study of paramagnetic iron and ruthenium metallacarboranes using cyclic voltammetry and matrix-activated laser desorption/ionization time-of-flight spectrometry

The complex investigation of paramagnetic (17-electron) iron and ruthenium closo-metallacarboranes with chelate diphosphine ligands 3,3-(Ph2P(CH)(n)PPh2)-3-Cl-closo-3,1,2-MC2B9H11 (M = Fe, n = 2, 3; Ru, n = 4), o-phenylenecycloboronated 3-Cl-3,3,8-[Ph2P(CH)(n)PPh-mu-(C6H4-o)]-1,2-R-2-closo-3,1,2-RuC2B9H10 (n = 3, 4; R = H or Me), and bis(o-cycloboronated) 3-Cl-3,3,7,8-[Ph2P(CH)(n)P-mu-C6H4-o)(2)]-closo-3,1,2-RuC2B9H9 (n = 4, 5) was performed using cyclic voltammetry and matrix-activated laser desorption/ionization time-of-flight (MALDI-TOF) spectrometry. Some diamagnetic iron and ruthenium exo-nido- and commo-complexes were studied using the same methods. A relationship between the redox potentials of the metallacarborane complexes and their stability and transformations under the MALDI-TOF conditions was established.