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Abstract
The carbenerhodium(I) complexes trans-[RhCl(CPh2)(L)2] (L = PPri3, 1a; SbPri3, 1b) react with PF3 by cleavage of the rhodium–carbene bond to give the corresponding PF3 derivatives trans-[RhCl(PF3)(L)2] 5a,b, in good yield. In contrast, treatment of the half-sandwich-type compound [(η5-C5H5)Rh(CPh2)(PPri3)], 2a, with both PF3 and P(OPh)3 leads to the migratory insertion of the CPh2 unit into one of the cyclopentadienyl C–H bonds to form the ring-substituted products [{η5-C5H4(CHPh2)}Rh(PX3)(PPri3)] (X = F, 6a; OPh, 6b). The molecular structures of 6a and 6b have been determined by X-ray crystallography. The reaction of the stibine complex [(η5-C5H5)Rh(CPh2)(SbPri3)], 2b, with PF3 proceeds by ligand displacement to afford the new carbenerhodium(I) compound [(η5-C5H5)Rh(CPh2)(PF3)], 7. The mechanism of the migratory insertion reaction is discussed.
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