Synthesis and characterization of new, modified terphenyl ligands: Increasing the rotational barrier for flanking rings

The synthesis and characterization of some new terphenyl ligands, modified by meta alkyl substitution on the central ring are described. The new ligands were designed for potential applications in the stabilization of novel low valent main group species or transition metal heteronuclear multiply bonded compounds. Compounds View the MathML source1-I-C6H1-2,6-Ph2-3,5-Pr2i (1), View the MathML source1-I-C6H1-2,6-Mes2-3,5-Pr2i (3) (Mes = 2,4,6-trimethylphenyl), View the MathML source1-I-C6H1-2,6-Trip2-3,5-Pr2i (5) (Trip = 2,4,6-triisopropylphenyl) and View the MathML source1-I-C6H1-2,6-Dipp2-3,5-Pr2i (6) (Dipp = 2,6-diisopropylphenyl) were obtained by addition of two equivalents of the corresponding aryl Grignard reagent to the benzyne intermediate generated by lithiation with BunLi of the starting material 2,4-dichloro-5-isopropylcumene, followed by quenching with iodine. The lithium salts of 2 and 4 were obtained treatment of the parent terphenyl iodides with one equivalent of nBuLi. All compounds were isolated as either colorless crystals or as white powders. They were characterized by 1H and 13C NMR spectroscopy and (in the case of 1 and 3) by X-ray crystallography. DFT calculations were performed on model terphenyl molecules in an attempt to estimate how much the rotation barriers of the flanking aryls can be influenced by substitution by alkyl groups of the two meta positions on central ring.