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- W2045229120 endingPage "4956" @default.
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- W2045229120 abstract "A family of bis(arylamino)chlorophosphines of the general formula (Ar = 4-MeO-C6H4, 3a; Ar = 2,4,6-Me3-C6H2, 3b; Ar = 2,6-(CHMe2)2-C6H3, 3c) has been prepared from PCl3 and the appropriate diamine. Steric interactions involving the 2,6-aryl substituents in 3b,c result in hindered rotation about the N−CAr bond, as evidenced by 1H NMR spectroscopy. Treatment of halophosphines 3a−c with AgOSO2CF3 (AgOTf) or Tl{B[3,5-(CF3)2-C6H3]4} (TlBArF) affords the cationic bis(arylamino)phosphenium compounds (4a−e; A = OTf, BArF), in high yield. Phosphenium cations 4a−d reversibly form adducts with trimethylphosphine. The structure of the phosphinophosphenium adduct 5c (Ar = 2,6-(CHMe2)2-C6H3) has been determined by single-crystal X-ray diffraction techniques, revealing both the steric influences of the 2,6-Ar substituents and the electronic nature of the bonding in 5. Treatment of Wilkinson's catalyst, RhCl(PPh3)3, with 1 equiv of 4a gives the first well-defined Rh phosphenium complex, (6), which is isolated in 80% yield. In contrast, treatment of Wilkinson's catalyst with 4c results in quantitative formation of [Rh(PPh3)3](OTf) and chlorophosphine 3c. The influence of the phosphenium N−Ar substituents is further evidenced by the analogous reaction between RhCl(PPh3)3 and mesityl-substituted 4b, which affords products analogous to 4a,c as well as the isomeric Rh phosphenium complex 7a, having cis PPh3 ligands. 31P NMR spectroscopic parameters for 6 and 7a,b are consistent with Rh−P multiple bonding." @default.
- W2045229120 created "2016-06-24" @default.
- W2045229120 creator A5001339135 @default.
- W2045229120 creator A5033721117 @default.
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- W2045229120 date "2000-10-28" @default.
- W2045229120 modified "2023-10-01" @default.
- W2045229120 title "Sterically Tunable Phosphenium Cations: Synthesis and Characterization of Bis(arylamino)phosphenium Ions, Phosphinophosphenium Adducts, and the First Well-Defined Rhodium Phosphenium Complexes" @default.
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- W2045229120 doi "https://doi.org/10.1021/om0005351" @default.
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