Copper(I) Bromide-Mediated Coupling of Imidazoles. Trapping and X-Ray Crystal Structures of the Reaction Intermediates

Solvothermal reaction of 5,10,10-trimethyl-bicyclo[2.2.1]-heptano-2-phenyl imidazole (TBHPI-H) with CuBr as a catalyst gave a one-dimensional infinite chain metal organic framework (MOF) (1) with the formulation {[(cis-(2C-2C)bi-TPHPI)2(trans-(2C-2C)Bi-TPHPI)](Cu2Br2)(Cu4Br4)} n . The (2C-2C)bi-TPHPI ligand formed in situ was shown to be present as both the cis and trans C(2)−C(2) coupling isomers, which was confirmed by LC-MS analysis revealing two peaks at 19.96 and 21.65 min containing a peak at 503 Da assignable to the [M + H]+ molecular ion fragment. To our knowledge, the trapping and structural characterization of such intermediates through formation of MOF complexes is unprecedented.