ja5020647_si_001.cif (218.04 kB)
Manipulating Magnetism: Ru25+ Paddlewheels Devoid of Axial Interactions
datasetposted on 2014-07-09, 00:00 authored by Gina M. Chiarella, F. Albert Cotton, Carlos A. Murillo, Karen Ventura, Dino Villagrán, Xiaoping Wang
Variable-temperature magnetic and structural data of two pairs of diruthenium isomers, one pair having an axial ligand and the formula Ru2(DArF)4Cl (where DArF is the anion of a diarylformamidine isomer and Ar = p-anisyl or m-anisyl) and the other one being essentially identical but devoid of axial ligands and having the formula [Ru2(DArF)4]BF4, show that the axial ligand has a significant effect on the electronic structure of the diruthenium unit. Variable temperature crystallographic and magnetic data as well as density functional theory calculations unequivocally demonstrate the occurrence of π interactions between the p orbitals of the chlorine ligand and the π* orbitals in the Ru25+ units. The magnetic and structural data are consistent with the existence of combined ligand σ/metal σ and ligand pπ/metal-dπ interactions. Electron paramagnetic resonance data show unambiguously that the unpaired electrons are in metal-based molecular orbitals.