[(C5Me5)2Zr(Me)(O(CH2)4NEt3)][B(C6F5)4] | 1260367-15-4

• 英文名称: [(C5Me5)2Zr(Me)(O(CH2)4NEt3)][B(C6F5)4]
• CAS: 1260367-15-4
• 化学式: C₂₄BF₂₀*C₃₁H₅₆NOZr
• 分子量: 1229.06
• InChiKey: HITLGUADYQWQAS-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

• 作为产物：
  描述：

  [(C5Me5)2Zr(Me)(THF)][B(C6F5)4] 、 三乙胺 以 四氢呋喃 为溶剂， 生成 [(C5Me5)2Zr(Me)(O(CH2)4NEt3)][B(C6F5)4]
  参考文献：
  名称：

  Catalyst Deactivation Reactions: The Role of Tertiary Amines Revisited

  摘要：

  Decamethylzirconocene cation [Cp*2ZrMe](+) (2) decomposes in bromobenzene-d(5) solution to generate sigma-aryl species [Cp*Zr-2(2-C6H4Br-kappa Br,C)][B(C6F5)(4)] (3). This a-bond metathesis reaction is catalyzed by tertiary amines via a two-step mechanism, in which the amine acts as a proton relay. In benzene-d(6) compound 2 decomposes via C H bond activation of one of the Cp* ligands to generate tucked-in compound [Cp*{eta(5):eta(1)-C5Me4(CH2)}Zr](+) (4). In the presence of Et3N, no formation of tucked-in compound 4 is observed, but instead an overall double C-H bond activation and C-N bond cleavage of the tertiary amine is observed, resulting in [Cp*Zr-2{C(Me)NEt-kappa C,N}](+) (6). A mechanism is proposed that nominates [Cp*2ZrNEt2](+) as an intermediate, the result of a C-H bond activation of Et3N, followed by beta-amide elimination. Attempted synthesis of this species by treatment of Cp*Zr-2(NEt2)Me with [Ph3C][B(C6F5)(4)] results, again, in formation of compound [6](+). The presence of Et3N also has an effect on the stability of THF adduct [Cp*2ZrMe(THF)](+) as the amine performs a nucleophilic THF ring-opening to generate [Cp*2ZrMe{O(CH2)(4)NEt3}](+) (7). The results show that amine coproducts, often generated in the synthesis of cationic transition-metal complexes, are not necessarily innocent.

  DOI：

  10.1021/om1007693