Lewis Acidity of Platinum(II)-Based Baeyer–Villiger Catalysts: An Electrochemical Approach

The electrochemical behavior of the Pt(II)-based Baeyer–Villiger catalysts of the general formulae [Pt(μ-OH)(P∩P)]2(BF4)2 (P∩P = dppe (1a), 2Fdppe (1 b), 4Fdppe (1c), dfppe (1d), dmpe (1e), depe (1f), dippe (1g), dtbpe (1h)) and [Pt(OH2)2(P∩P)](OTf)2 (P∩P = dppe (2a), 2Fdppe (2b), 4Fdppe (2c), dfppe (2d)) is reported. They exhibit irreversible reduction processes whose potentials reflect the Lewis acidity of the metal centres, showing (for the aromatic diphosphine complexes) overall relations with the number of fluorine atoms, with JPt–P, with the ν(Ctriple bond; length of mdashN) coordination shift of a ligand isocyanide probe and with the catalytic activity. Single-crystal X-ray diffraction analyses were carried out for [Pt(μ-OH)(4Fdppe)]2(BF4)2 (1c) and [Pt(μ-OH) (dippe)]2(BF4)2 (1g)