Interaction of triphenylphosphineplatinum(0) complexes with organic azides and some carbonylation reactions

The reactions of triphenylphosphineplatinum(0) complexes with organic azides have been investigated in various solvents. With sulphonyl azides the major products are of the type Pt(PPh₃)₂(X)(NHSO₂R)(X = OH, N₃, NHSO₂R; R = Ph, MeC₆H₄) besides other by-products. Similar complexes are formed with Me·C₆H₄·SO₂-NNaCl,3H₂O (chloramine T). In absence of solvents compounds of formula Pt(PPh₃)₂(N₂SO₂R)₂(R = Ph, MeC₆H₄) have been obtained. With acyl and aroyl azides only Pt(PPh₃)₂(N₃)₂ and Pt(PPh₃)₂(N₃)(NCO) have been recovered. The compounds (PPh₃)₂Pt(N₃)(X)(X = N₃, NCO, NHSO₂·C₆H₄Me) react in alcohols with carbon monoxide under mild conditions yielding Pt(PPh₃)₂(NCO)(CO₂R)(R = Me, Et, Prⁱ, Prⁿ). Some possible mechanisms of these reactions are discussed.