Crystal of meso- p-tolyl-porphyrinato copper(II) Cu(tptp) and di-cation ion-pair complex [H 4tptp] 2+[CF 3SO 3] 2− formation during the reaction of Cu(CF 3SO 3) 2 with meso- p-tolyl-porphyrin in CDCl 3

Abstract

In the NMR and ESR time-scale of this experiment, an attempt was made to prepare the copper sitting-atop (SAT) species [Cu(H 2tptp)] 2+ by the reaction of Cu(CF 3SO 3) 2 with meso- p-tolyl-porphyrin (H 2tptp) in CDCl 3; however, this led to the formation of meso- p-tolyl-porphyrinatocopper(II) Cu(tptp) and the protonated porphyrin [H 4tptp] 2+[CF 3SO 3] 2 − ( 2a). Previous researchers might have misinterpreted the SAT [Cu(H 2tpp)] 2+ complex as being a single component instead of a mixture of [H 4tpp] 2+[CF 3SO 3] 2 − ( 1) and Cu(tpp) for a similar reaction between 5,10,15,20-tetraphenylporphyrin H 2tpp and Cu(CF 3SO 3) 2 in CH 3CN. This work determines the crystal structure of Cu(tptp) and its hyperfine constants a Cu=94.0 G and a N=15.8 G using ESR. The crystal structure of [H 4tptp] 2+[CH 3SO 3] 2 − ( 3) is reported and employed to simulate the groupings of [H 4tptp] 2+ and CF 3SO 3 − in the di-cation ion-pair complex 2a.