Syntheses of organorhodium(I) and organ oplatinum(II) compounds by decarboxylation

Summary Decarboxylation of metal carboxylates provides a route to numerous main group element organometallics^{(1, 2)}, and to several transition metal organometaliics in which the central metal has a closed shell (d¹⁰) configuration^{(1, 2)}, e.g. organocopper(I) derivatives^(3–5). Extensions to compounds with non-d¹⁰ central metals are restricted to some organonickel(II) derivatives⁽⁶⁾. In addition,-allylplatinum(II) complexes have been prepared by decarboxylation of allyloxycarbonyl-andN-allylcarbamoylplatinum(II) compounds⁽⁷⁾, but the reactants are not carboxylato complexes since the -C(O)O-groups arecarbon-bonded to platinum. We now report decarboxylation syntheses of some organorhodium(I) and organoplatinum(II) compounds from suitable metal carboxylates.Reaction oftrans-RhCl(CO)(Ph₃P)₂ with some thallous polyfluorobenzoates, TlO₂CR, in pyridine at room temperature (R = C₆F₅) or on heating (R = C₆F₅,p-HC₆F₄ or m-HC₆F₄) resulted in decarboxylation and formation of the corresponding organorhodium compound (Table).