Long-wavelength charge transfer absorption energies of isomeric complexes (L)M(CO)4 (L = 3,3'-bipyridazine, 2,2'- and 4,4'-bipyrimidine, 2,2'-bipyrazine; M = Cr, Mo, W) were measured in various solvents and compared with those for corresponding 2,2'-bipyridine complexes. Linear correlations of energies of absorption max. with solvent parameters EMLCT* (MLCT = metal to ligand charge transfer) revealed that the solvent dependence Du/DEMLCT* within the L series increases with decreasing abs. charge transfer transition energy in a given solvent, i.e. with increasing back-donation into the ligand p* orbital. Complexes of the most strongly back-bonding ligand, 4,4'-bipyrimidine, thus display by far the most pronounced solvent dependence, with Du/DEMLCT* 4100 cm-1 for the molybdenum system. on SciFinder(R)
%0 Journal Article
%1 Ernst.1986c
%A Ernst, Sylvia
%A Kurth, Yvonne
%A Kaim, Wolfgang.
%D 1986
%J Journal of Organometallic Chemistry
%K backbonding backbonding;bipyrimidine backbonding;biyridazine backbonding;chromium backbonding;molybdenum backbonding;tungsten bipyrazine complex diimine metal solvatochromism
%N 2
%P 211--215
%R 10.1016/0022-328X(86)80084-5
%T Correlation between solvatochromism and back-bonding in four isomeric (a-diimine)M(CO)4 complexes (M = Cr, Mo, W)
%V 302
%X Long-wavelength charge transfer absorption energies of isomeric complexes (L)M(CO)4 (L = 3,3'-bipyridazine, 2,2'- and 4,4'-bipyrimidine, 2,2'-bipyrazine; M = Cr, Mo, W) were measured in various solvents and compared with those for corresponding 2,2'-bipyridine complexes. Linear correlations of energies of absorption max. with solvent parameters EMLCT* (MLCT = metal to ligand charge transfer) revealed that the solvent dependence Du/DEMLCT* within the L series increases with decreasing abs. charge transfer transition energy in a given solvent, i.e. with increasing back-donation into the ligand p* orbital. Complexes of the most strongly back-bonding ligand, 4,4'-bipyrimidine, thus display by far the most pronounced solvent dependence, with Du/DEMLCT* 4100 cm-1 for the molybdenum system. on SciFinder(R)
@article{Ernst.1986c,
abstract = {Long-wavelength charge transfer absorption energies of isomeric complexes (L)M(CO)4 (L = 3,3'-bipyridazine, 2,2'- and 4,4'-bipyrimidine, 2,2'-bipyrazine; M = Cr, Mo, W) were measured in various solvents and compared with those for corresponding 2,2'-bipyridine complexes. Linear correlations of energies of absorption max. with solvent parameters EMLCT* (MLCT = metal to ligand charge transfer) revealed that the solvent dependence \textgreek{Du}/\textgreek{D}EMLCT* within the L series increases with decreasing abs. charge transfer transition energy in a given solvent, i.e. with increasing back-donation into the ligand \textgreek{p}* orbital. Complexes of the most strongly back-bonding ligand, 4,4'-bipyrimidine, thus display by far the most pronounced solvent dependence, with \textgreek{Du}/\textgreek{D}EMLCT* 4100 cm-1 for the molybdenum system. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Ernst, Sylvia and Kurth, Yvonne and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/21b27f9eb73434bb5053eae2c37d2fece/huebleriac},
doi = {10.1016/0022-328X(86)80084-5},
interhash = {d5756cbef44e72b341e4380ca7cba75f},
intrahash = {1b27f9eb73434bb5053eae2c37d2fece},
journal = {Journal of Organometallic Chemistry},
keywords = {backbonding backbonding;bipyrimidine backbonding;biyridazine backbonding;chromium backbonding;molybdenum backbonding;tungsten bipyrazine complex diimine metal solvatochromism},
number = 2,
pages = {211--215},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Correlation between solvatochromism and back-bonding in four isomeric (\textgreek{a}-diimine)M(CO)4 complexes (M = Cr, Mo, W)},
volume = 302,
year = 1986
}