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Substituted silastannatetrahydro-s-indacenes as cyclopentadienyl transfer agents in the synthesis of silanediyl bridged zirconocene complexes

Substituted silastannatetrahydro-s-indacenes as cyclopentadienyl transfer agents in the synthesis of silanediyl bridged zirconocene complexes

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HÜTTENHOFER, Mario, Marc-Heinrich PROSENC, Ursula RIEF, Frank SCHAPER, Hans-Herbert BRINTZINGER, 1996. Substituted silastannatetrahydro-s-indacenes as cyclopentadienyl transfer agents in the synthesis of silanediyl bridged zirconocene complexes. In: Organometallics. 15(22), pp. 4816-4822. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om960305f

@article{Huttenhofer1996Subst-23760, title={Substituted silastannatetrahydro-s-indacenes as cyclopentadienyl transfer agents in the synthesis of silanediyl bridged zirconocene complexes}, year={1996}, doi={10.1021/om960305f}, number={22}, volume={15}, issn={0276-7333}, journal={Organometallics}, pages={4816--4822}, author={Hüttenhofer, Mario and Prosenc, Marc-Heinrich and Rief, Ursula and Schaper, Frank and Brintzinger, Hans-Herbert} }

Rief, Ursula Substituted silastannatetrahydro-s-indacenes as cyclopentadienyl transfer agents in the synthesis of silanediyl bridged zirconocene complexes Prosenc, Marc-Heinrich 2013-06-24T16:48:31Z Hüttenhofer, Mario The substituted silastannatetrahydro-s-indacenes meso-Me<sub>2</sub>Si(t-BuC<sub>5</sub>H<sub>3</sub>)<sub>2</sub>SnMe<sub>2</sub>, meso-Me<sub>2</sub>Si(Me<sub>2</sub>C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>SnMe<sub>2</sub>, and meso-Me<sub>2</sub>Si(Me-i-PrC<sub>5</sub>H<sub>2</sub>)<sub>2</sub>SnMe<sub>2</sub>, prepared from the corresponding silanediyl-bridged dicyclopentadienide dilithium salts by reaction with Me<sub>2</sub>SnCl<sub>2</sub>, were structurally characterized by X-ray diffraction and by <sup>1</sup>H-NMR in solution. These cyclic stannanediyl compounds react with ZrCl<sub>4</sub> to give selectively the meso diastereomers of the ansa-zirconocene complexes Me<sub>2</sub>Si(3-t-BuC<sub>5</sub>H<sub>3</sub>)<sub>2</sub>ZrCl<sub>2</sub>, Me<sub>2</sub>Si(2,4-Me<sub>2</sub>C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrCl<sub>2</sub>, and Me<sub>2</sub>Si(2-Me-4-i-PrC<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrCl<sub>2</sub>, respectively. Reaction of Me<sub>2</sub>Si(2-Me-4-t-BuC<sub>5</sub>H<sub>2</sub> <sup>-</sup> Li<sup>+</sup>)<sub>2</sub> with Me<sub>2</sub>SnCl<sub>2</sub> gives, instead of Me<sub>2</sub>Si(Me-t-BuC<sub>5</sub>H<sub>2</sub>)<sub>2</sub>SnMe<sub>2</sub>, the distannyl derivative Me<sub>2</sub>Si(2-Me-4-t-BuC<sub>5</sub>H<sub>2</sub>-1-SnMe<sub>2</sub>Cl)<sub>2</sub>. This compound reacts with ZrCl<sub>4</sub> to give a 1:1 mixture of the rac and meso isomers of Me<sub>2</sub>Si(2-Me-4-t-BuC<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrCl<sub>2</sub>. Ring-opened, racemic distannyl compounds are formed also from meso-Me<sub>2</sub>Si(t-BuC<sub>5</sub>H<sub>3</sub>)<sub>2</sub>SnMe<sub>2</sub>, meso-Me<sub>2</sub>Si(Me<sub>2</sub>C<sub>5</sub>H<sub>2</sub>)<sub>2</sub>SnMe<sub>2</sub>, and meso-Me<sub>2</sub>Si(Me-i-PrC<sub>5</sub>H<sub>2</sub>)<sub>2</sub>SnMe<sub>2</sub> with excess Me<sub>2</sub>SnCl<sub>2</sub>. Competition between Me<sub>2</sub>SnCl<sub>2</sub> and Zr centers for reaction with stannylcyclopentadiene units appears to limit the overall stereoselectivity of the ansa-zirconocene complex formation. Brintzinger, Hans-Herbert Hüttenhofer, Mario Schaper, Frank 2013-06-24T16:48:31Z Prosenc, Marc-Heinrich Rief, Ursula Brintzinger, Hans-Herbert eng Organometallics ; 15 (1996), 22. - S. 4816-4822 1996 Schaper, Frank deposit-license

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