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<p>The various esters of the phosphoric and phosphorous acids have been obtained directly from white phosphorus and aliphatic (or aromatic) alcohols under aerobic atmosphere in the presence of the CuX₂ or FeX₃ (X = Cl, NO₃, C₃H₇CO₂) salts. Irrespective of the variable nature of the used alcohols and catalysts, trialkyl(aryl) phosphates and dialkyl phosphites are a major products, whereas trialkyl(aryl) phosphites and dialkyl phosphates are a minor products of the phosphorylation process. Thanks to the presence of catalysts, the possible side reaction route of the radical chain oxidation of white phosphorus by oxygen to phosphorus oxides has been precluded. A comparison between the catalytic properties of CuX₂ and FeX₃ has been done. Although both of them have been found an efficient catalysts for the syntheses, the Cu(II) salts are active at 50-65 °C, whereas the Fe(III) based catalytic systems become competitive in terms of catalytic efficiency when reaction is carried out at 70-90 °C. Aromatic alcohols are characterised by less reactivity in this catalytic reaction as compared with an aliphatic ones. The same coordinative redox mechanism of the oxidative P-O coupling of P₄to ROH in the presence of both Cu(II) and Fe(III) catalysts has been proposed. Relevant steps of the catalytic cycle including the complexation of both white phosphorus and alcohol molecules to metal ion, the reduction of catalyst by white phosphorus, and the oxidation of reduced form of catalyst by oxygen have been also considered.</p>