Inorganic Chemistry, Vol.35, No.2, 289-296, 1996
Solvatochromism of Monomolybdenum and Dimolybdenum Coordination-Compounds of Dipyridyloctatetraene and Linear Solvation Energy Relationship Models Based on the Kamlet-Taft and Drago Scales of Solvent Polarity
The heteroleptic molybdenum complexes [{Mo(NO)Tp*X}(n)(L-L)][Tp* = HB(3,5-Me(2)C(3)HN(2))(3); X = Cl, I; L-L 4-NC5H4(CH=CH)(4)C5H4N-4’, n = 1, 2; X = Cl; L-L = {4,4’-NC5H4CH=CHC(Me)=CHCH=}(2), n = 2] have a low energy absorbance in their electronic spectra which exhibits solvatochromic shifts. These have been analyzed quantitatively by means of linear solvation energy relationships based on Kamlet-Taft solvatochromism parameters, as well as on Drago’s "unified scale of solvent polarity". Each of these approaches leads to satisfactory linear models, in qualitative agreement with one another. The solvatochromism is due to a combination of increased solvent dipolarity/polarizability and solvent-to-solute hydrogen bonding, each preferentially stabilizing polar ground states compared with less polar excited states. The latter originate from metal-to-ligand charge transfer. Quantitatively, the Drago and Kamlet-Taft models differ somewhat. The former are statistically slightly better than those based on Kamlet-Taft parameters.