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

Thomas B. Rauchfuss; D. Max Roundhill

doi:10.1021/ja00817a014

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

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Abstract

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 language	English (US)
Pages (from-to)	3098-3105
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	96
Issue number	10
DOIs	https://doi.org/10.1021/ja00817a014
State	Published - May 1 1974
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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@article{3185c98d055d431f95300e7453108b84,

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

abstract = "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.",

author = "Rauchfuss, {Thomas B.} and Roundhill, {D. Max}",

year = "1974",

month = may,

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doi = "10.1021/ja00817a014",

language = "English (US)",

volume = "96",

pages = "3098--3105",

journal = "Journal of the American Chemical Society",

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

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