Abstract
The reaction of benzoyl chloride with [Rh(dppp) 2]Cl at 190°C and with [Rh(dppp)Cl] 1 or 2 at 25°C where dppp 1,3-bis(diphenylphosphino)propane has been examined. In both cases the five coordinate compound RhCl 2(COPh)-(dppp) was rapidly formed and isolated in high yield. This compound does not undergo phenyl migration to RhCl 2(CO)(Ph)(dppp) even upon warming to 190°C in benzoyl chloride solution and no decarbonylation products are observed. This is in marked contrast to the reaction of RhCl(PPh 3) 3 with benzoyl chloride where the migrated product RhCl 2(CO)(Ph)(PPh 3) 2 is formed with the eventual reductive elimination of chlorobenzene. The single crystal X-ray analysis of RhCl 2(COPh)(dppp) has been carried out ( R 0.036). The compound is square pyramidal with the COPh group in the apical position. The Rh—C bond distance of 1.992(3) Å is short for a Rh III—Cσ bond and indicates d π → π ★ back bonding.
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