The solventless synthesis of tris(pyrazolyl)phenylmethane ligands of formula C6H5C(PzR2)3 (R = H, Me), starting from PhCCl3 and 3,5-dimethylpyrazole (PzMe2) or pyrazole (Pz) was performed. The sterically crowded C6H5C(PzMe2)3 is thermally transformed into the bis(pyrazolyl)(p-pyrazolyl)phenylmethane ligand PzMe2-C6H4CH(PzMe2)2. In this compound both PzMe2 rings are linked through the N-atom to the methine C-atom. At higher temperatures, the binding mode of PzMe2 changes from N1 to C4. All transformations occurred via quinonoid carbocation intermediates that undergo an aromatic electrophilic substitution on the 4-position of PzMe2. Reaction conditions were established to obtain five tris(pyrazolyl)phenylmethane ligands in moderate to good yields. 1H- and 13C-NMR spectroscopy and X-ray diffraction of single crystals support the proposed structures.
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