TY - JOUR
T1 - Synthesis and Reactions of Nucleophilic Complexes of Rhodium(I) Containing o-(Diphenylphosphino)-N, N-dimethylaniline
AU - Rauchfuss, Thomas B.
AU - Roundhill, D. Max
PY - 1974/5/1
Y1 - 1974/5/1
N2 - 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.
AB - 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.
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U2 - 10.1021/ja00817a014
DO - 10.1021/ja00817a014
M3 - Article
AN - SCOPUS:33847804759
VL - 96
SP - 3098
EP - 3105
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 10
ER -