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ansa-Titanocene and -Zirconocene η2-Alkyne Complexes -Synthesis, Spectral Characteristics, and X-ray Crystal Structure (1996)

Peulecke, Normen ; Lefeber, Claudia ; Ohff, Andreas ; [weitere]

Weinheim : Wiley-Blackwell

Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 959-962

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ISSN: 0009-2940

Schlagwort(e): ansa-Zirconocenes ; ansa-Titanocenes ; Alkyne complexes ; Pyridine ligands ; Chemistry ; Inorganic Chemistry

Quelle: Wiley InterScience Backfile Collection 1832-2000

Thema: Chemie und Pharmazie

Notizen: The reduction of the complex [(η5-C5H4)-ansa-(η5-C5H4)]TiCl2 with magnesium in the presence of Me3SiC2-SiMe3 in THF at room temperature gives the ansa-titanocone alkyne complex [(η5-C5H4)-ansa-(η5-C5H4)]Ti(η2-Me3SiC2-SiMe3) (ansa = Me2Si-O-SiMe2, 1). The similar pyridine-stabilized zirconium complexes could be obtained by analogous reactions and addition of pyridine: [(η5-C5H4)-ansa-(η5-C5H4)]Zr(L)(η2-Me3SiC2SiMe3) (ansa = Me2Si-O-SiMe2, L = pyridine: 2; ansa = SiMe2, L = pyridine: 3). All complexes were characterized by spectroscopic methods. An X-ray structure determination of complex 3 was conducted, and the data were compared to those of the complexes rac-(EB-HI)Zr(L)(η2-Me3SiC2SiMe3) [L = (S)-(-)-nicotine: 6, EBHI = ethylenebis(tetrahydroindenyl)] and Cp2Zr(py)(Me3SiC2-SiMe3).

Zusätzliches Material: 2 Ill.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1002/cber.19961290813

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Digitale Medien

The First Titanacyclic Five-Membered Cumulene. Synthesis, Structure, and Reactivity (1995)

Burlakov, Vladimir V. ; Ohff, Andreas ; Lefeber, Claudia ; [weitere]

Weinheim : Wiley-Blackwell

Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 967-971

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ISSN: 0009-2940

Schlagwort(e): Titanocene ; Diyne ; Cumulene ; Titanacyclopentadiene ; Chemistry ; Inorganic Chemistry

Quelle: Wiley InterScience Backfile Collection 1832-2000

Thema: Chemie und Pharmazie

Notizen: The first five-membered titanacyclic cumulene (5) was prepared by treatment of the titanocene generator Cp2Ti(Me3SiC2SiMe3) with the di-tert-butylbutadiyne in a molecular one-to-one ratio. The reaction of 5 with “Cp2Zr” or of the analogous complex with “Cp2Ti” leads to cleavage of the central C-C bond in the metallacyclocumulene complexes to afford the same product, the heterodimetallic ρ, π,-alkynyl-bridged titanocene-zirconocene complex Cp2Zr(μ-η1η2-C≡CtBu)Cp2Ti(μ-η1η2-C≡CtBu) (6), in which each alkynyl group is π-bonded to one and π-bonded to the other metal as shown by X-ray diffraction studies. In solution the two alkynyl groups become equivalent. The coupling reaction of “Cp2Ti” with bis(trimethylsilyl)butadiyne in a one-to-two molecular ratio leads to the unsymmetrically substituted titanacyclopentadiene (7).

Zusätzliches Material: 2 Ill.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1002/cber.19951281002

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