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• W2321806287 abstract "The dilithium bis(cyclopentadienide) species Li2{Me2Si[C5H2-2,4-(CHMe2)2]2} (Li2Ip) reacts with ScCl3(THF)3 to afford rac-IpScCl·LiCl(THF)2 (1) and [meso-IpSc(μ2-Cl)]2 (2) and with YCl3(THF)3.5 to afford rac-IpYCl·LiCl(THF)2 (3) and [meso-IpY(μ2-Cl)]2 (4). Metalation with both scandium and yttrium chlorides yields the metallocene chlorides in approximately 3:1 racemic:meso ratios. Reaction of IpH2 with Zr(NMe2)4 yields exclusively meso-IpZr(NMe2)2 (9). Treatment of 1 or 2 with allylmagnesium bromide affords the allyl complexes rac-IpSc(η3-C3H5) (5) and meso-IpSc(η3-C3H5) (6) and with crotylmagnesium chloride affords rac-IpSc(η3-C3H4Me) (7) and meso-IpSc(η3-C3H4Me) (8). Diastereomerically pure rac dichlorometalate compounds (1 or 3) or pure meso chloro dimers (2 or 4) undergo spontaneous isomerization upon dissolution in THF-d8 with reversion back to a 3:1 racemic:meso ratio. Isomerization of 5 and 6 is observed in THF-d8, above 55 °C, affording an equilibrium ratio of ∼2:1 racemic:meso isomers. While spontaneous isomerization of 5, 6, 7, or 8 is very slow at room temperature, various salts and Grignard reagents promote isomerization even at room temperature; the isomerizations are not accelerated by light. The proposed mechanism for racemic−meso isomerization involves heterolytic dissociation of one cyclopentadienide ligand from the metal, rotation around that Si−Cp- bond, and recoordination on the opposite face, effecting net epimerization. X-ray diffraction studies have been performed on rac-IpScCl·LiCl(THF)2 (1), [meso-IpY(μ2-Cl)]2 (4), and meso-IpZr(NMe2)2 (9)." @default.
• W2321806287 created "2016-06-24" @default.
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• W2321806287 date "1998-10-13" @default.
• W2321806287 modified "2023-10-18" @default.
• W2321806287 title "Racemic−Meso Interconversion for <i>ansa</i>-Scandocene and <i>ansa</i>-Yttrocene Derivatives. Molecular Structures of <i>r</i><i>ac-</i>{Me₂Si[η⁵-C₅H₂-2,4-(CHMe₂)₂]₂}ScCl·LiCl(THF)₂, [<i>m</i><i>eso</i>-{Me₂Si[η⁵-C₅H₂-2,4-(CHMe₂)₂]₂}Y(μ₂-Cl)]₂, and <i>m</i><i>eso-</i>{Me₂Si[η⁵-C<sub>5</…" @default.
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• W2321806287 doi "https://doi.org/10.1021/om980349j" @default.
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