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Ligand perturbation of the molecular and electronic structures of quadruply bonded dimers. The Crystal structures of Mo/sub 2/Br/sub 4/(PMe/sub 3/)/sub 4/ and Mo/sub 2/I/sub 4/(PMe/sub 3/)/sub 4/, and the vibrational and electronic spectra of a series of M/sub 2/X/sub 4/L/sub 4/ complexes

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00236a019· OSTI ID:7149327
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The authors have recently undertaken an investigation of the spectroscopic, magnetic, photophysical, and photochemical properties of a large number of derivatives of the M/sub 2/X/sub 4/L/sub 4/ type (M = Mo, W; X = Cl, Br, I; L = uncharged sigma-donor ligand), which form one of the largest subclasses of quadruply bonded dimers. One of the more striking findings of these studies is that parameters such as (delta ..-->.. delta*) transition energies, electronic absorption and emission band shapes and intensities, and the rates of radiative and nonradiative excited state decay, which are properties associated with the formally metal-metal-localized manifold of electronic states, display a marked sensitivity to the nature of ligands X and L. In order to determine whether this ligand dependence is also reflected in the ground-state properties of these complexes, as well as to provide a structural benchmark for analyzing ligand perturbations of their excited states, they determined the crystal structures of two such derivatives, Mo/sub 2/Br/sub 4/(PMe/sub 3/)/sub 4/ and Mo/sub 2/I/sub 4/(PMe/sub 3/)/sub 4/, and the vibrational and electronic spectra of a series of M/sub 2/X/sub 4/L/sub 4/ complexes. These results are reported herein, along with a general interpretation of the ligand sensitivity of the energies and intensities of the (delta ..-->.. delta*) transitions of quadruply bonded dimers.
Research Organization:
California Institute of Technology, Pasadena
OSTI ID:
7149327
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:2; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
ARSENIC COMPOUNDS
BINDING ENERGY
BROMIDES
BROMINE COMPOUNDS
CHLORIDES
CHLORINE COMPOUNDS
CRYSTAL STRUCTURE
DATA
ELECTRONIC STRUCTURE
ENERGY
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
IODIDES
IODINE COMPOUNDS
LASER SPECTROSCOPY
LATTICE PARAMETERS
LIGANDS
MOLYBDENUM BROMIDES
MOLYBDENUM CHLORIDES
MOLYBDENUM COMPOUNDS
MOLYBDENUM IODIDES
NUMERICAL DATA
ORGANIC ARSENIC COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
RAMAN SPECTROSCOPY
REFRACTORY METAL COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS
VIBRATIONAL STATES