Electrosynthesis and X‐ray Crystallographic Structure of Zn II meso ‐Triaryltriphenylphosphonium Porphyrin and Structural Comparison with Mg II meso ‐Triphenylphosphonium Porphine

The electrochemical oxidation of Zn II 5 , 15 ‐bis( p ‐tolyl)‐ 10 ‐phenylporphyrin ( 1‐Zn ) in the presence of triphenylphosphine (PPh 3 ) leads to the meso ‐substituted triphenylphosphonium porphyrin, coordinated by one P(O)Ph 3 molecule [ 1‐Zn‐PPh 3 + ,PF 6 – ·P(O)Ph 3 ] in good yield (84 %). This cationic porphyrin was characterized by NMR, MALDI‐TOF mass spectrometry, UV/Vis. absorption spectroscopy and X‐ray diffraction analyses. The molecular structure of this compound was compared with already published meso ‐ and β‐triphenylphosphonium porphyrins but also with an unpublished X‐ray crystallographic structure of Mg II 5‐triphenylphosphoniumporphine ( MgP‐PPh 3 + ,PF 6 – ) previously obtained by electrosynthesis.