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 · Wed Jan 21 00:00:00 EST 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00236a019· OSTI ID:7149327

Hopkins, M D; Schaefer, W P; Bronikowski, M J; Woodruff, W H; Miskowski, V M; Dallinger, R F; Gray, H B

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), Vol. 109:2
• Country of Publication: United States
• Language: English

Related Subjects

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