Ta(CHSiMe3CH2CH2)[2,6-(Me2NCH2)-C6H3]Cl(O-tBu) | 157261-90-0

• 英文名称: Ta(CHSiMe3CH2CH2)[2,6-(Me2NCH2)-C6H3]Cl(O-tBu)
• CAS: 157261-90-0
• 化学式: C₂₂H₄₂ClN₂OSiTa
• 分子量: 595.075
• InChiKey: ZRSPJMPVCOZRGI-UHFFFAOYSA-M

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：

  乙烯 、 Ta(=CHSiMe3)[2,6-(Me2NCH2)-C6H3]Cl(O-tBu) 以 氘代苯 为溶剂， 生成 Ta(CHSiMe3CH2CH2)[2,6-(Me2NCH2)-C6H3]Cl(O-tBu)
  参考文献：
  名称：

  含有芳基二胺观众配体的钽烷氧化物配合物的构型偏好和以亚烷基为中心的反应性

  摘要：

  Transmetalation of Ta(=CH-t-Bu){C6H3(CH2NMe2)2-2,6}Cl2 with LiO-t-Bu or KOMe affords monoalkoxide complexes Ta(=CH-t-Bu){C6H3(CH2NMe2)2-2,6}CI(OR) (R = t-Bu, Me) in moderate yield. The tert-butoxide complex Ta(=CH-t-Bu)){C6H3(CH2NMe2)2-2,6}Cl(O-t-Bu) reacts with (trimethylsilyl)ethene to afford a (trimethylsilyl)methylidene analogue via a quantitative alkene metathesis reaction. Transmetalation of Ta(=CH-t-Bu)Cl(O-t-Bu)2(PMe3) with 1/2 equiv of [Li{C6Hs(CH2NMe2)2-2,6}]2 gives the dialkoxide complex Ta(=CH-t-Bu){C6H3(CH2NMe2)2-2,6}(O-t-Bu)2, 3d, in moderate yield. Complex 3d belongs to space group P1BAR with a = 9.3519(5) angstrom, b = 9.4443(3) angstrom, c = 18.1110(9) angstrom, alpha = 90.432(3)-degrees, beta = 100.241(4)-degrees, gamma = 116.593(3)-degrees, and Z = 2. The pentacoordinate tantalum center in Sd has a distorted trigonal bipyramidal geometry with one of the NMe2 units of the C,N-bidentate bonded aryldiamine (Ta-N(2) = 2.415(3) angstrom) and one of the alkoxide ligands in axial positions, while the second o-CH2NMe3 substituent is free (Ta...N(l) = 3.426(3) angstrom) but still trans-oriented to the alkylidene carbon atom. Complex 3d reacts with (trimethylsilyl)ethene to afford its (trimethylsilyl)methylidene analogue. A dialkoxide complex, Ta(=CH-t-Bu)(C6H4CH2NMe2-2)(O-t-Bu)2, 3b, that is related to 3d but which contains only one o-amino substituent, can be prepared in a one-pot procedure by a sequence of transmetalation reactions starting from Ta(=CH-t-Bu)Cl3(THF)2 (THF = tetrahydrofuran), Zn(C6H4CH2NMe2-2)2, and LiO-t-Bu. All alkoxide complexes are fluxional in solution at room temperature and undergo dissociation/association processes involving the coordinative Ta-N bonds of the arylamine ligands.

  DOI：

  10.1021/om00020a044