The Involvement of Metal-to-CO Charge Transfer and Ligand-Field Excited States in the Spectroscopy and Photochemistry of Mixed-Ligand Metal Carbonyls. A Theoretical and Spectroscopic Study of [W(CO)4(1,2-Ethylenediamine)] and [W(CO)4(N,N‘-Bis-alkyl-1,4-diazabutadiene)]

2003 ◽  
Vol 125 (15) ◽  
pp. 4580-4592 ◽  
Author(s):  
Stanislav Záliš ◽  
Ian R. Farrell ◽  
Antonín Vlček
Keyword(s):  
Charge Transfer ◽  
Spectroscopic Study ◽  
Excited States ◽  
Mixed Ligand ◽  
Ligand Field ◽  
Metal Carbonyls

The Character of Low-Lying Excited States of Mixed-Ligand Metal Carbonyls. TD-DFT and CASSCF/CASPT2 Study of [W(CO)4L] (L = ethylenediamine, N,N'-dialkyl-1,4-diazabutadiene) and [W(CO)5L] (L = pyridine, 4-cyanopyridine)

2003 ◽  
Vol 68 (1) ◽  
pp. 89-104 ◽  
Author(s):  
Stanislav Záliš ◽  
Antonín Vlček ◽  
Chantal Daniel
Keyword(s):  
Excited States ◽  
Substitution Effect ◽  
Electronic Transitions ◽  
Ligand Field ◽  
Metal Carbonyls ◽  
Electron Density Redistribution ◽  
Time Resolved ◽  
Model Complex ◽  
Td Dft ◽  
Time Resolved Infrared Spectroscopy

This contribution presents the results of the TD-DFT and CASSCF/CASPT2 calculations on [W(CO)4(MeDAB)] (MeDAB = N,N'-dimethyl-1,4-diazabutadiene), [W(CO)4(en)] (en = ethylenediamine), [W(CO)5(py)] (py = pyridine) and [W(CO)5(CNpy)] (CNpy = 4-cyanopyridine) complexes. Contrary to the textbook interpretation, calculations on the model complex [W(CO)4(MeDAB)] and [W(CO)5(CNpy)] show that the lowest W→MeDAB and W→CNpy MLCT excited states are immediately followed in energy by several W→CO MLCT states, instead of ligand-field (LF) states. The lowest-lying excited states of [W(CO)4(en)] system were characterized as W(COeq)2→COax CT excitations, which involve a remarkable electron density redistribution between axial and equatorial CO ligands. [W(CO)5(py)] possesses closely-lying W→CO and W→py MLCT excited states. The calculated energies of these states are sensitive to the computational methodology used and can be easily influenced by a substitution effect. The calculated shifts of [W(CO)4(en)] stretching CO frequencies due to excitation are in agreement with picosecond time-resolved infrared spectroscopy experiments and confirm the occurrence of low-lying M→CO MLCT transitions. No LF electronic transitions were found for either of the complexes studied in the region up to 4 eV.

Photosubstitution reactivity of a series of pentacarbonylpyridinotungsten(0) complexes having ligand field or charge-transfer lowest excited states

1976 ◽  
Vol 98 (14) ◽  
pp. 4105-4109 ◽  
Author(s):  
Mark S. Wrighton ◽  
Harmon B. Abrahamson ◽  
David L. Morse
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Ligand Field

Metal-to-Metal Electron-Transfer Emission in Cyanide-Bridged Chromium−Ruthenium Complexes: Effects of Configurational Mixing Between Ligand Field and Charge Transfer Excited States

2008 ◽  
Vol 47 (23) ◽  
pp. 10921-10934 ◽  
Author(s):  
Yuan-Jang Chen ◽  
Onduru S. Odongo ◽  
Patrick G. McNamara ◽  
Konrad T. Szacilowski ◽  
John F. Endicott
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Excited States ◽  
Ruthenium Complexes ◽  
Ligand Field ◽  
Metal Electron
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