Steric control of substituted phenoxide ligands on product structures of uranyl aryloxide complexes

A series of uranyl aryloxide complexes has been prepared via metathesis reactions between [UO(2)Cl(2)(THF)(2)](2) and di-ortho-substituted phenoxides. Reaction of 4 equiv of KO-2,6-(t)()Bu(2)C(6)H(3) with [UO(2)Cl(2)(THF)(2)](2) in THF produces the dark red uranyl compound, UO(2)(O-2,6-(t)()Bu(2)C(6)H(3))(2)(THF)(2).THF, 1. Single-crystal X-ray diffraction analysis of 1 reveals a monomer in which the uranium is coordinated in a pseudooctahedral fashion by two apical oxo groups, two cis-aryloxides, and two THF ligands. A similar product is prepared by reaction of KO-2,6-Ph(2)C(6)H(3) with [UO(2)Cl(2)(THF)(2)](2) in THF. Single-crystal X-ray diffraction analysis of this compound reveals it to be the trans-monomer UO(2)(O-2,6-Ph(2)C(6)H(3))(2)(THF)(2), 2. Dimeric structures result from the reactions of [UO(2)Cl(2)(THF)(2)](2) with less sterically imposing aryloxide salts, KO-2,6-Cl(2)C(6)H(3) or KO-2,6-Me(2)C(6)H(3). Single-crystal X-ray diffraction analyses of [UO(2)(O-2,6-Cl(2)C(6)H(3))(2)(THF)(2)](2), 3, and [UO(2)Cl(O-2,6-Me(2)C(6)H(3))(THF)(2)](2), 4, reveal similar structures in which each U atom is coordinated by seven ligands in a pseudopentagonal bipyramidal fashion. Coordinated to each uranium are two apical oxo groups and five equatorial ligands (3, one terminal phenoxide, two bridging phenoxides, and two nonadjacent terminal THF ligands; 4, one terminal chloride, two bridging phenoxides, and two nonadjacent terminal THF ligands). Apparently, the phenoxide ligand steric features exert a greater influence on the solid-state structures than the electronic properties of the substituents. Emission spectroscopy has been utilized to investigate the molecularity and electronic structure of these compounds. For example, luminescence spectra taken at liquid nitrogen temperature allow for a determination of the dependence of the molecular aggregation of 3 on the molecular concentration. Electronic and vibrational spectroscopic measurements have been analyzed to examine trends in emission energies and stretching frequencies. However, comparison of the data for compounds 1-4 reveals that the innate electron-donating capacity of phenoxide ligands is only subtly manifest in either the electronic or vibrational energy distributions within these molecules.