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Stabilisierung niederkoordinierter M(CO)-Bausteine: Synthese und Reaktivität von {(η⁵-C₅H₄SiMe₃)₂Hf(C≡CPh)₂}M(CO) (M = Ni, Co)

Journal of Organometallic Chemistry. Bd. 465. H. 1-2. Amsterdam: Elsevier 1994 S. 283 - 287

Erscheinungsjahr: 1994

ISBN/ISSN: 1872-8561

Publikationstyp: Zeitschriftenaufsatz

Sprache: Deutsch

Doi/URN: 10.1016/0022-328X(94)87067-5

Volltext über DOI/URN

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Inhaltszusammenfassung


The synthesis and reactivity of the dinuclear compounds (L(2)Hf(C=CPh)(2))M(CO)(L = eta(5)-C(5)H(4)SiMe(3); M = Ni: III; M = Co: V) are described. The organometallic diyne PhC=C-L(2)Hf-C=CPh (I) reacts with Ni(CO)(4) (II) or Co-2(CO)(8) (IV) to afford in high yields III or V, respectively. In III and V, both phenylethynyl units are eta(2)-side-on coordinated to M(CO) building blocks. Along with the paramagnetic complex V, compound L(2)Hf(C=CPh) [mu-(eta(2)-C=CPh)Co-2(CO)(6)] (VI) can be isola...The synthesis and reactivity of the dinuclear compounds (L(2)Hf(C=CPh)(2))M(CO)(L = eta(5)-C(5)H(4)SiMe(3); M = Ni: III; M = Co: V) are described. The organometallic diyne PhC=C-L(2)Hf-C=CPh (I) reacts with Ni(CO)(4) (II) or Co-2(CO)(8) (IV) to afford in high yields III or V, respectively. In III and V, both phenylethynyl units are eta(2)-side-on coordinated to M(CO) building blocks. Along with the paramagnetic complex V, compound L(2)Hf(C=CPh) [mu-(eta(2)-C=CPh)Co-2(CO)(6)] (VI) can be isolated. Reaction of VI with more Co-2(CO)(8) (IV) yields the compound L(2)Hf[mu-(eta(2)-C=CPh)Co-2(CO)(6)](2) (VII). The reaction of L(2)M(C=CR)(2) (M = Hf, R = Ph: Ia; M = Ti, R = Ph: Ib; M = Ti, R = SiMe(3): Ic) with Fe-2(CO)(9) (VIII) yields L(2)M[(eta(2)-C=CR)Fe(CO)(4)](2) (M = Hf, R = Ph: IXa; M = Ti, R = Ph: IXb; M = Ti, R = SiMe(3): IXc). In IX each of the two C=CR groups is eta(2) -side-on coordinated to the 16-electron fragment Fe(CO)(4). When III is treated with P(OR)(3) (R=CH3: Xa; R=(C3H7)-C-i: Xb) carbonyl substitution is observed to form (L(2)Hf(C=CPh)(2))Ni[P(OR)(3)] (R = CH3: XIa; R =(C3H7)-C-i: XIb). The identity of all new compounds is confirmed by analytical and spectroscopic (IR, H-i NMR, C-13 NMR, P-31 NMR, MS) data. Additionally, the structures of I and V were established by X-ray diffraction. » weiterlesen» einklappen

  • Cobalt
  • Hafnium
  • Iron
  • Nickel
  • Silicon
  • Titanium

Autoren


Lang, Heinrich (Autor)
Herres, Mathias (Autor)

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