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Title: Manipulating Magnetism: Ru-2(5+) Paddlewheels Devoid of Axial Interactions

Variable-temperature magnetic and structural data of two pairs of diruthenium isomers, one pair having an axial ligand and the formula Ru-2(DArF)(4)Cl (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 [Ru-2(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 pi interactions between the p orbitals of the chlorine ligand and the pi* orbitals in the Ru-2(5+) units. The magnetic and structural data are consistent with the existence of combined ligand sigma/metal sigma and ligand p pi/metal-d pi interactions. Electron paramagnetic resonance data show unambiguously that the unpaired electrons are in metal-based molecular orbitals.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [3]
  1. Texas A&M University
  2. University of Texas at El Paso
  3. ORNL
Publication Date:
OSTI Identifier:
1154877
DOE Contract Number:
DE-AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 136; Journal Issue: 27
Research Org:
Oak Ridge National Laboratory (ORNL)
Sponsoring Org:
SC USDOE - Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
TRANSITION-METAL-COMPLEXES; EFFECTIVE CORE POTENTIALS; SUPRAMOLECULAR ASSEMBLIES; MOLECULAR CALCULATIONS; ELECTRONIC-STRUCTURES; DIRUTHENIUM