METALLORGANISCHE VERBINDUNGEN DES IRIDIUMS UND RHODIUMS. XXIX. CO2-TRANSFORMATIONEN AM TRIPHOSPHANRHODIUM(I)-KOMPLEX Rh(4-MeC6H4)

Article abstract of DOI:10.1016/S0022-328X(00)99522-6

The arylrhodium(I) complex Rh(Ar)L (Ar=4-MeC6H4, L=t-BuP(CH2CH2Ch2PPh2)2; I), prepared from RhClL and tolyllithium, reacted with carbon dioxide to give RhL (II) and Rh<<*>(O)>(Ar)L (IV).In the presence of ethanol, the ethylcarbonate RhL (III) was obtained.Reaction of I with CO2/O2 yielded the peroxocarbonato derivative Rh<*>(Ar)L (V) which was characterized by X-ray diffraction. 13C and 31P NMR spectroscopy showed the C2O4 compound IV, dissolved in pyridine, to disintegrate to Rh<*>(Ar)L(IVa) and Rh(Ar)(Py)L (IVb).The CO4 derivative V was found to interact with the same solvent to produce the carbonate IVa and pyridine-N-oxide.