Synthesis, Structure, and Complexation of an S-Shaped Double Azahelicene with Inner-Edge Nitrogen Atoms.

An S-shaped double azahelicene (1) was synthesized in excellent yield by a palladium-catalyzed double dehydrogenative C-H coupling reaction. The stereochemistry of 1 was confirmed to be dl by single-crystal X-ray diffraction analysis. Selective formation of dl-1 was attributed to the isomerization of the kinetically controlled product (meso-1) into the more thermodynamically stable dl-1 under the applied reaction conditions. dl-1 can coordinate to palladium(II) in a bidentate trans-chelating fashion, which was confirmed by X-ray absorption fine structure (XAFS) as well as by X-ray photoelectron spectroscopy (XPS), diffuse reflectance (DR) UV/Vis, and far-infrared (FIR) absorption spectroscopy. Theoretical calculations of palladium complex 16 revealed a weak attractive interaction between palladium and carbon atoms on the central dimethoxynaphthalene core, which could facilitate a disproportionation between a trans-chelating (dl-1)⋅PdCl2 complex and PdCl2 to form 16.