The axial ligation of [Mo2]4+ compounds remains an underdeveloped area of chemistry, impacting the usefulness of these compounds in fields such as catalysis. We have previously demonstrated through the synthesis and characterization of LiMo2(SNO5)4Cl (SNO5 = monothiosuccinimidate) that axial ligation can be enhanced when a Lewis acid, such as Li+, is held in close proximity to the dimolybdenum core by a suitable supporting ligand. SNO5 is suitable in this regard because it contains both a soft base (S), which preferentially binds to a soft acid such as Mo2+, and a hard base (O), which preferentially binds to a hard Lewis acid. Now, we present a variety of [Mn+Mo2(SNO5)4Cl]n-1+ (Mn+ = Na+, Ca2+, Sr2+, Y3+, Ce3+) compounds that have been successfully synthesized either through self-assembly methods or by cationic substitution, using LiMo2(SNO5)4Cl as the starting material. Using this set of compounds, the chemical and electrostatic effects on [Mo2]4+ axial ligation due to the charge of the Lewis acid as well as the proximity of the Lewis acid to the dimolybdenum core have been evaluated using X-ray crystallography, electrochemistry, UV-vis spectroscopy, and DFT calculations.

Effects of cationic charge and charge proximity in Lewis acid enhanced axial ligation of [Mo2]4+ compounds

249th National Meeting (2015)

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