buta-1,3-diene;tert-butyl-[cyclopenta-2,4-dien-1-yl(dimethyl)silyl]azanide;titanium(2+) | 350250-47-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: buta-1,3-diene;tert-butyl-[cyclopenta-2,4-dien-1-yl(dimethyl)silyl]azanide;titanium(2+)
• CAS: 350250-47-4
• 化学式: C₄H₆*C₁₁H₁₉NSi*Ti
• 分子量: 295.336
• InChiKey: JMBYYHBXOIERNH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  buta-1,3-diene;tert-butyl-[cyclopenta-2,4-dien-1-yl(dimethyl)silyl]azanide;titanium(2+) 、 三(五氟苯基)硼烷 以 甲苯 为溶剂， 以82%的产率得到[(C5H4)Si(CH3)2(NC(CH3)3)Ti(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

文献信息

• Preparation and Structural Characterization of <i>ansa</i>-Mono(cyclopentadienyl)dimethylsilylamido Group 4 Metal Butadiene Complexes. Observation of a Tetranuclear Structure for [(C₅H₄)SiMe₂(N-t-Bu)]Zr(C₄H₆) Featuring Bridging Butadiene Ligands
  作者：Joachim W. Strauch、Jeffrey L. Petersen

  DOI：10.1021/om001090j

  日期：2001.6.1

  The metathetical reactions of [(C5H4)SiMe2(N-t-Bu)]MCl2, M = Ti, Zr, with [Mg(C4H6)(THF)2]n afford the respective group 4 metal butadiene complexes, [(C5H4)SiMe2(N-t-Bu)]M(C4H6). The solution NMR and X-ray crystallographic data for [(C5H4)SiMe2(N-t-Bu)]Ti(C4H6) indicate that the butadiene moiety adopts a symmetrical prone structure consistent with a Ti(II) π-diene bonding representation. Alternatively

  [（C 5 H 4）SiMe 2（Nt-Bu）] MCl 2（M = Ti，Zr）与[Mg（C 4 H 6）（THF）2 ] n的复分解反应提供相应的第4组金属丁二烯配合物，[（C 5 H 4）SiMe 2（Nt-Bu）] M（C 4 H 6）。[（C 5 H 4）SiMe 2（Nt-Bu）] Ti（C 4 H 6）的溶液NMR和X射线晶体学数据）表明丁二烯部分采用与Ti（II）π-二烯键表示相符的对称倾向结构。或者，其Zr类似物的溶液和固态结构明显不同。观察到的[（C 5 H 4）SiMe 2（Nt-Bu）] Zr（C 4 H 6）的反丁二烯和中丁二烯质子的化学位移分散体在溶液中支持氧化锆环戊烯结构，其固态结构该化合物实际上是四核的。四[（C 5 H ^ 4）森达2（N-叔丁基）]的[（C锆单元5 ħ 4）森达2（N-叔丁基）]锆（C 4ħ 6）} 4由晶体施加的相关小号4旋转轴和经由