Correlation between solvatochromism and back-bonding in four isomeric (a-diimine)M(CO)4 complexes (M = Cr, Mo, W)
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Journal of Organometallic Chemistry 302 (2): 211--215 (1986)

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)
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