Molecular structure of dimethoxo(tetraphenylporphyrinato)phosphorus(V) chloride and one-step hydrolysis of its derivative hydroxomethoxo(tetraphenylporphyrinato)phosphorus(V) ion: [P(tpp)(Me)(OH] +

Abstract

The title compound dimethoxo(tetraphenylporphyrinato)phosphorus(V) chloride, [P(tpp)(OMe) 2] +Cl −, has been synthesized and its molecular structure determined by X-ray analysis. The molecule [P(tpp)(OMe) 2] +Cl −, displays and octahedral coordination geometry for the phosphorus atom. The displacement of the phorphorus atom from the porphyrin mean plane was 0.0834 Å. The geometry around the phosphorus centre of the [P(tpp)(OMe) 2] +Cl − molecule has PO(1) = 1.634(4), PO(2) = 1.630(5) and PNp = 1.825(4) Å. The hydrolysis of its derivative hydroxomethoxo(tetraphenylporphyrinato)phosphorus(V) ion, [P(tpp)(OMe)(OH)] + was studied by NMR spectroscopy. The use of a limited amount of water in CDCl 3 allowed the hydrolysis product, dihydroxo (tetraphenylporphyrinato)phosphorus(V) ion, [P(tpp)(OH) 2] +, to be identified. The results show that the hydrolysis is a one-step reaction, with an absolute rate constant k = (2.34±0.23) × 10 4 s − M −1 at 24°C.