Selective Lithiation and Phosphane-Functionalization of [(η-CH)Ti(η-CH)] (Troticene) and Its Use for the Preparation of Early-Late Heterobimetallic Complexes.

The cycloheptatrienyl-cyclopentadienyl sandwich complex [η-CH)Ti(η-CH)) (troticene) can be dilithiated (once at each ring) or selectively monolithiated, either at the seven- or five-membered ring, depending on the reaction conditions. Treatment of the resulting lithiotroticenes with CIPPh2 afforded...

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Publicado en:Journal of the American Chemical Society Vol. 131; no. 46; pp. 17014 - 17024
Autores principales: Mohapatra, Swagat K., Büschel, Susanne, Daniliuc, Constantin, Jones, Peter G., Tamm, Matthias
Formato: Artículo
Publicado: American Chemical Society 11/25/2009
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 11/25/2009
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      pub: American Chemical Society
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        10.1021/ja9080056
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        atl: Selective Lithiation and Phosphane-Functionalization of [(η-CH)Ti(η-CH)] (Troticene) and Its Use for the Preparation of Early-Late Heterobimetallic Complexes.
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        au:
          Mohapatra, Swagat K.
          Büschel, Susanne
          Daniliuc, Constantin
          Jones, Peter G.
          Tamm, Matthias
        affil: Institut für Anorganische und Analytische Chemie, Technische Universität Carolo-Wilhelmina, Hagenring 30, 38106 Braunschweig, Germany
      su:
        X-ray diffraction
        Ferrocene
        Chemical reactions
        Metal complexes
        Molecular structure
      sug:
        subj:
          X-ray diffraction
          Ferrocene
          Chemical reactions
          Metal complexes
          Molecular structure
      ab: The cycloheptatrienyl-cyclopentadienyl sandwich complex [η-CH)Ti(η-CH)) (troticene) can be dilithiated (once at each ring) or selectively monolithiated, either at the seven- or five-membered ring, depending on the reaction conditions. Treatment of the resulting lithiotroticenes with CIPPh2 afforded the corresponding troticenyl-phosphanes [(η-CHPPh)Ti(η-CHPPh)] (1), [(η-CHPPh)Ti(η-CH)] (2), or [(η-CH)Ti(η-CHPPh)] (3). The use of nBuLi/N,W,W,W',N'-pentamethyldiethylenetriamine (pmdta) allowed us to isolate the lithium complexes [(η-CHLi)Ti(η-CHLi)]·pmdta (4) and [(η-CH)Ti(η-CHLi)]-pmdta (5), which were structurally characterized by X-ray diffraction analyses. Reaction of the monophosphane 3 with Mo(CO) and [(tht)AuCI] (tht = tetrahydrothiophene) afforded the heterobimetallic complexes [(3)Mo(CO)] (6) and [(3)AuCI] (7) and also the trimetallic species [(3)AuCl] (8). The reaction of trans-[PtCI(SEt)] with the diphosphane 1 led to the formation of cis-[(1)PtCI] (9), whereas the complexes trans-[(2)PtCI] (10) and trans-[(3)PtCI] (11) were isolated by reaction of two equivalents of the monophosphanes 2 and 3 with trans-[PtCI(SEt)]. The X-ray crystal structures of 6-11 are also reported.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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