Detailed herein are synthetic studies aimed at isolating low-coordinate iron complexes supported by encumbering m-terphenyl isocyanides. Using the sterically hindered CNArDipp2 and CNArMes2 (ArDipp2 = 2,6-(2,6-[i-Pr]2C6H3)2C6H3, ArMes2 = 2,6-(2,4,6-Me3C2H6)2C6H3) ligands, many promising synthetic avenues have been uncovered. Heating mixtures of FeX2 (X = Br, I), CNArDipp2 and Fe0 yielded complexes with the form FeX2(CNArDipp2)2 and FeX2(THF)2(CNArDipp2), depending on the solvent used. Reactions between CNArDipp2 and CNArMes2 with Fe(COT)2 (COT = 1,3,5,7-cyclooctatetraene) have yielded Fe(CNArDipp2)2(COT2) and Fe(COT)(CNArMes2)3, respectively.  Reductive pathways have also yielded new products.  When FeI2 is treated with CNArDipp2 and Mg0 the product is Fe(CNArDipp2)(CN(2-(2,6[i-Pr]2C6H3)-6-(?6-2,6[i-Pr]2C6H3)).  The most promising result comes from the reaction of FeBr2 with CNArMes2 and Na/Hg.  The resulting product is Na2[Fe(CNArMes2)4] which is an isolobal analogue to [Fe(CO)4]2-. Reactivity studies aimed at the generating [Fe(CNAr)n]x complexes that span a large variety of oxidation states are discussed.

Iron complexes supported by sterically encumbering m-terphenyl isocyanides

243rd National Meeting (2012)

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