(η3-tris(3-tert-butylpyrazolyl)hydroborato)Mg(η1-OC(=CH2)C(CH3)3) | 137743-98-7

• 英文名称: (η3-tris(3-tert-butylpyrazolyl)hydroborato)Mg(η1-OC(=CH2)C(CH3)3)
• CAS: 137743-98-7
• 化学式: C₂₇H₄₅BMgN₆O
• 分子量: 504.81
• InChiKey: XNUUBAJVLJBEIB-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：

  η3-tris(3-tert-butylpyrazolyl)hydroborato(MgCH2CH3) 在 CH₃I 作用下， 以 氘代苯 、 苯 为溶剂， 生成 (η3-tris(3-tert-butylpyrazolyl)hydroborato)Mg(η1-OC(=CH2)C(CH3)3)
  参考文献：
  名称：

  [Tris(pyrazolyl)hydroborato]magnesium alkyl derivatives: reactivity studies

  摘要：

  The reactivity of a series of 4-coordinate [tris(pyrazolyl)hydroborato]magnesium alkyl derivatives, {eta-3-HB(3-Bu(t)pz)3}MgR and {eta-3-HB(3,5-Me2pz)3}MgR (3-Bu(t)pz = 3-C3N2Bu(t)H2, 3,5-Me2pz = 3,5-C3N2Me2H; R = CH3, CH2CH3, (CH2)3CH3, CH(CH3)2, C(CH3)3, CH = CH2, C6H5, CH2SiMe3), has been investigated. The complexes {eta-3-HB(3,5-Me2pz)3}MgR undergo ligand redistribution reactions, analogous to the Schlenk equilibrium, to give the 6-coordinate sandwich complex {eta-3-HB-(3,5-Me2pz)3}2Mg. In contrast, the 4-coordinate magnesium alkyl derivatives supported by the more sterically demanding tris(3-tert-butylpyrazolyl)hydroborato ligand, {eta-3-HB(3-Bu(t)pz)3}MgR, are stable with respect to the formation of {eta-3-HB(3-Bu(t)pz)3}2Mg. The alkyl complexes {eta-3-HB(3-Bu(t)pz)3}MgR are useful precursors for a variety of other 4-coordinate complexes, including {eta-3-HB(3-Bu(t)pz)3}MgX (X = C = CC6H5, C = CSiMe3, OEt, OPr(i), OBu(t), OPh, OCH2SiMe3, OSiMe3, OOBu(t), NHPh, SH, SCH3, Cl, Br, I, NCO, NCS). CO2 inserts into the Mg-C bond of {eta-3-HB(3-Bu(t)pz)3}MgCH3 to give the eta-1-acetato complex {eta-3-HB(3-Bu(t)pz)3}Mg{eta-1-OC(O)CH3}. In contrast, the reactions with the ketones CH3C(O)CH3 and CH3C(O)Bu(t) do not result in insertion to give the alkoxide derivatives, but preferentially give the enolate complexes {eta-3-HB(3-Bu(t)pz)3}Mg{eta-1-OC(= CH2)CH3} and {eta-3-HB(3-Bu(t)pz)3}Mg{eta-1-OC(= CH2)Bu(t)}, accompanied by the elimination of methane. Insertion of O2 into the Mg-R bond of the complexes {eta-3-HB(3-Bu(t)pz)3}MgR (R = CH3, CH2CH3, CH(CH3)2, C(CH3)3) results in formation of the alkylperoxo derivatives {eta-3-HB(3-Bu(t)pz)3}MgOOR, which have been characterized by the use of O-17 NMR spectroscopy. In contrast, the reaction of the magnesium (trimethylsilyl)methyl complex {eta-3-HB(3-Bu(t)pz)3}MgCH2SiMe3 with O2 gives the trimethylsiloxide derivative {eta-3-HB(3-Bu(t)pz)3}MgOSiMe3 as result of facile cleavage of the Si-C bond upon autoxidation. The molecular structures of {eta-3-HB(3,5-Me2pz)3}2Mg and {eta-3-HB(3-Bu(t)pz)3}MgCl have been determined by X-ray diffraction. {Eta-3-HB-(3,5-Me2pz)3]2Mg is triclinic, P1BAR (No. 2), a = 8.837 (3) angstrom, b = 10.223 (3) angstrom, c = 10.772 (2) angstrom, alpha = 63.92 (3)-degrees, beta = 85.24 (2)-degrees, gamma = 79.87 (2)-degrees, V = 860.4 (4) angstrom3, Z = 1. {Eta-3-HB(3-Bu(t)pz)3}MgCl is orthorhombic, Pnma (No. 62), a = 16.048 (7) angstrom, b = 16.006 (3) angstrom, c = 9.840 (1) angstrom, V = 2527 (1) angstrom3, Z = 4.

  DOI：

  10.1021/ja00028a051