Add time:07/16/2019         Source:sciencedirect.com

Chlorotris(triphenylphosphine)rhodium, RhCl(PPh3)3 undergoes thermal decomposition above 140°C in solution and in the solid state to yield biphenyl. Rhodium complexes with para-substituted triphenylphosphine ligands form exclusively 4,4′-disubstituted biphenyls. Mixtures of two complexes RhCl(PAr3)3 and RhCl(PAr′3)3 form the crossed diaryl ArAr′ and two non-crossed compounds (Ar)2 and (Ar′)2. The mechanism is assumed to involve dissociation of RhCl(PPh3)3 into PPh3 and solvated RhCl(Pph3)2 followed by oxidative addition of the liberated phosphine to the latter bis-triphenylphosphine compound. Evidence for a phenyl-rhodium intermediate has been provided by phenylation of styrene by RhCl(PPh3)3. In an independent process, RhCl(PPh3)3 forms benzene by an ortho-metallation route.

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