| 767288-51-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• CAS: 767288-51-7
• 化学式: C₄H₆*C₁₁H₁₉NSi*Zr
• 分子量: 338.68
• InChiKey: SWFYDANTCDJWIQ-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  、 三(五氟苯基)硼烷 以 甲苯 为溶剂， 以76%的产率得到[(C5H4)Si(CH3)2(NC(CH3)3)Zr(μ-C4H6)B(C6F5)3]
  参考文献：
  名称：

  Structural and Spectroscopic Evidence for Intramolecular Agostic M···H−C and Dative Zr←F−C(ortho) Interactions in the Zwitterionic Metal Complexes [(C₅H₄)SiMe₂(N-t-Bu)]M(+)(μ-C₄H₆)B(−)(C₆F₅)₃, M = Ti, Zr

  摘要：

  The reactions of equimolar amounts of [(C5H4)SiMe2(N-t-Bu)]M(C4H6) (M = Ti, Zr) and B(C6F5)(3) proceed cleanly with the formation of the zwitterionic complexes [(C5H4)SiMe2(N-t-Bu)]M(+)(mu-C4H6)B(-)(C6F5)(3). X-ray structural analyses of these novel compounds indicate that the pi-allyl unit within the asymmetrical bridging cis-butadiene moiety adopts the Z-configuration. The structure of the zwitterionic Ti-betaine complex is stabilized by a pair of Ti(+)H-...-CB(-) agostic interactions, whereas the structure of the Zr analogue features a dative Zr<--F-C(ortho) interaction with a Zr-F distance of 2.324(1) Angstrom and a single Zr(+)H-...-CB(-) agostic interaction. Variable-temperature F-19 NMR data show that the broad ortho-F resonance for the three freely rotating perfluorophenyl groups at room temperature separates upon cooling (193 K) to produce six distinct signals at delta -124.8, -129.6, -131.8, -133.4, -135.7, and -189.2, consistent with the coordination of an ortho-F atom to the electrophilic Zr center. From a line shape analysis the free energy barrier for disruption of this Zr<--F-C(ortho) interaction is estimated to be ca. 9.8 kcal/mol (T-c = 223 K).

  DOI：

  10.1021/om040057k