Hexakispyrazolylethane: New Strategy for Stabilization of Hexaarylethane

Hexakis(4-trimethylsilylpyrazol-1-yl)ethane was synthesized by the oxidative dimerization of tris(4-trimethylsilylpyrazol-1-yl)methane. Single-crystal X-ray structural analysis of hexakis(4-trimethylsilylpyrazol-1-yl)ethane showed that the ethane C-C bond (1.623(4) Å) is shorter than that in hexaphenylethane (1.67(3) Å). In solution, hexakis(4-trimethylsilylpyrazol-1-yl)ethane existed as a single species, contrastive that conventional hexaphenylethanes can keep the central C-C bond only by the aid of additional bridges between the two triarylmethyl units. Theoretical calculations indicated that the tris(pyrazol-1-yl)methyl radical, which is anticipated to be under equilibrium with hexakis(pyrazol-1-yl)ethane, is less stable than trityl radicals due to lack of delocalization of the radicals. Furthermore, introduction of pyrazole groups allowed additional bridging between the two triarylmethyl moieties through metal coordination to the adjacent N atoms: hexakis(4-trimethylsilylpyrazol-1-yl)ethane exhibited unique coordination to three Ag atoms affording a hexaarylethane analog bearing three N-Ag-N bridges.