Iridium Phosphinidene Complexes: A Comparison with Iridium Imido Complexes in Their Reaction with lsocyanides.

18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cpª(Xy—N≡C)lr=PAr] (Ar = Mesª, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cpª(Xy—N≡C)IrPArC=NR]. Their structures were ascertaine...

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Publicado en:Journal of the American Chemical Society Vol. 131; no. 37; pp. 13531 - 13538
Autores principales: Aktas, Halil, Mulder, Jos, de Kanter, Frans J. J., Slootweg, J. Chris, Schakel, Marius, Ehlers, Andreas W., Lutz, Martin, Spek, Anthony L., Lammertsma, Koop
Formato: Artículo
Publicado: American Chemical Society 9/23/2009
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 9/23/2009
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        10.1021/ja9048509
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        atl: Iridium Phosphinidene Complexes: A Comparison with Iridium Imido Complexes in Their Reaction with lsocyanides.
      aug:
        au:
          Aktas, Halil
          Mulder, Jos
          de Kanter, Frans J. J.
          Slootweg, J. Chris
          Schakel, Marius
          Ehlers, Andreas W.
          Lutz, Martin
          Spek, Anthony L.
          Lammertsma, Koop
        affil:
          Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteir Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, Netherlands
          Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University, Padualaan 8, 3584 CH Utrecht, Netherlands
      su:
        Iridium spectra
        Density functionals
        X-ray diffraction
        Isocyanides
        Nitrogen
        Nucleophilic reactions
      sug:
        subj:
          Iridium spectra
          Density functionals
          X-ray diffraction
          Isocyanides
          Nitrogen
          Nucleophilic reactions
      ab: 18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cpª(Xy—N≡C)lr=PAr] (Ar = Mesª, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cpª(Xy—N≡C)IrPArC=NR]. Their structures were ascertained by X-ray diffraction. Density functional theory investigations on model structures revealed that the iridaphosphirane complexes are formed from the addition of the isocyanide to 16-electron species [Cpªlr=PAr] forming first complex 3 that subsequently reacts with another isocyanide to give the products following a different pathway than its nitrogen analogue [Cpªlr≡Nt-Bu] 1.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2009
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