Synthesis and Reactions of Nucleophilic Complexes of Rhodium(I) Containing o-(Diphenylphosphino)-N, N-dimethylaniline

Thomas B. Rauchfuss, D. Max Roundhill

Research output: Contribution to journalArticlepeer-review


The complexes [Rh(PN)2]X (X = Cl, PF6, SbF6, BPh4, ClO4) where PN is o-(diphenylphosphino)-N,N-dimethylaniline are described. The trans addition of Cl2 and CH3I gives [RhCl2(PN)2]X and [RhCH3I(PN)2]X. Oxygen and cyanogen add to give [RhO2(PN)2]X and [Rh(CN)2(PN)2]X where the adduct groups occupy cis positions. [Rh(PN)2]X adds carbon monoxide to form [Rh(PN)2(CO)2]X where the dimethylamino arms of the chelate are displaced. Heating the dicarbonyl in boiling toluene favors the reverse reaction. [Rh(PN)2(CO)2]PF6 reacts with CH3I to give RhI2(COCH3)CO(PN) because of the likely presence of iodide in the reaction medium. The low conductivity of RhCl(PN)2 is due to ion pairing. The complexes RhClCO(PN), RhCl(PF3)(PN), and Rh-(C5H8O2)(PN) have been isolated. RhClCO(PN) is converted into [Rh(PN)2(CO)2]PF6 by reaction with PN and NH4PF6 under a CO atmosphere. RhClCO(PN) adds allyl chloride to form RhCl2(σ-C3H5)CO(PN). RhClCO-(PN) reacts with CH3I in the presence of NaI to give RhI2(COCH3)CO(PN). Two separate isomers of the acetyl complex have been isolated. The number of nonequivalent N-methyl resonances for the coordinated dimethylamino group is used to identify the stereochemistry of many of the above complexes. Ir2Cl2(cyclooctene)4 reacts with PN and NH4PF6 to give [IrHCl(PN)2]PF6.

Original languageEnglish (US)
Pages (from-to)3098-3105
Number of pages8
JournalJournal of the American Chemical Society
Issue number10
StatePublished - May 1 1974
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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