η3-tris(3-tert-butylpyrazolyl)hydroborato(Mg(CH(CH3)2)) | 125950-40-5

• 英文名称: η3-tris(3-tert-butylpyrazolyl)hydroborato(Mg(CH(CH3)2))
• CAS: 125950-40-5
• 化学式: C₂₄H₄₁BMgN₆
• 分子量: 448.746
• InChiKey: DKMADLKQLOCELN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  η3-tris(3-tert-butylpyrazolyl)hydroborato(Mg(CH(CH3)2)) 在 O₂ 作用下， 以 苯 为溶剂， 以>99的产率得到η3-tris(3-tert-butylpyrazolyl)hydroborato(MgOO(CH(CH3)2))
  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
• 作为产物：
  描述：

  potassium hydrotris(3-tert-butylpyrazol-1-yl)borate 、 异丙基氯化镁 以 乙醚 为溶剂， 以75%的产率得到η3-tris(3-tert-butylpyrazolyl)hydroborato(Mg(CH(CH3)2))
  参考文献：
  名称：

  [Tris(pyrazolyl)hydroborato]magnesium alkyl derivatives: synthetic and structural studies

  摘要：

  A series of solvent-free, monomeric, (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, CH(CH3)2, C(CH3)3, CH2(CH2)2CH3, CH2Si(CH3)3, CH = CH2, C6H5), have been prepared by the reaction of the appropriate dialkylmagnesium compound with either the potassium or thallium derivatives of the respective tris(pyrazolyl)hydroborato ligand. The molecular structures of the complexes {eta-3-HB(3-Bu(t)pz)3}MgCH3, {eta-3-HB(3-Bu(t)pz)3}MgCH(CH3)2, and {eta-3-HB(3,5-Me2pz)3}MgCH2Si(CH3)3 have been determined by X-ray diffraction, which shows that in each case the complexes are monomeric with 4-coordinate magnesium centers and eta-3-coordinate tris(pyrazolyl)hydroborato ligands. {eta-3-HB(3-Bu(t)pz)3}MgCH3 is orthorhombic, Pnma, a = 16.362 (4) angstrom, b = 15.920 (5) angstrom, c = 9.824 (4) angstrom, and Z = 4. {eta-3-HB(3-Bu(t)pz)3}MgCH(CH3)2 is orthorhombic, Pnma, a = 17.171 (2) angstrom, b = 15.893 (7) angstrom, c = 10.034 (3) angstrom, and Z = 4. {eta-3-HB(3,5-Me2pz)3}MgCH2Si(CH3)3 is monoclinic, C2/c, a = 23.897 (8) angstrom, b = 8.010 (2) angstrom, c = 30.072 (8) angstrom, and Z = 8. In contrast to the clean reactions of the thallium and potassium tris(pyrazolyl)hydroborato derivatives with R2Mg, the corresponding reactions with Grignard reagents are more complex as a result of competition between Mg-R and Mg-X bond metathesis. The product distribution is dependent upon both RMgX and the tris(pyrazolyl)hydroborato reagent. Thus, for the thallium complex Tl{eta-3-HB(3-Bu(t)pz)3}, chloro and bromo Grignard reagents favor alkyl ligand metathesis and the formation of {eta-3-HB(3-Bu(t)pz)3}MgX, whereas the iodo Grignard reagent CH3MgI favors halide ligand metathesis and the formation of {eta-3-HB(3-Bu(t)pz)3}MgCH3. However, the selectivity of these reactions with Grignard reagents may be altered by the use of the potassium reagent K{HB(3-Bu(t)pz)3}, and thus, primary and secondary Grignard reagents react with K{HB(3-Bu(t)pz)3} to give the alkyl derivatives {eta-3-HB(3-Bu(t)pz)3}MgR as the principal products.

  DOI：

  10.1021/om00050a036

文献信息

• Insertion of oxygen into the magnesium-carbon bonds of the alkyl derivatives {.eta.3-HB(3-tert-Bupz)3}MgR [R = CH3, CH2CH3, CH(CH3)2, C(CH3)3]. Formation of alkylperoxo derivatives and oxygen atom transfer
  作者：Runyu Han、Gerard Parkin

  DOI：10.1021/ja00165a063

  日期：1990.4

  describe the quantitative insertion of dioxygen into the Mg-C bond of the alkyl complexes η 3 -HB-(3-Bu t pz) 3 }MgR (3-Bu t pz=3-C 3 N 2 Bu t H 2 ; R=CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 ), to give alkylperoxo derivatives η 3 -HB(3-Bu t pz) 3 }MgOOR, and the conversion of the alkylperoxo complexes to alkoxo derivatives, η 3 -HB(3-Bu t pz) 3 }MgOR, by oxygen atom transfer

  我们描述了分子氧定量插入烷基配合物 η 3 -HB-(3-Bu t pz) 3 }MgR (3-Bu t pz=3-C 3 N 2 Bu t H 2 ; R=CH 3 , CH 2 CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 )，得到烷基过氧衍生物η 3 -HB(3-Bu t pz) 3 }MgOOR，以及烷基过氧配合物与烷氧衍生物 η 3 -HB(3-Bu t pz) 3 }MgOR，通过氧原子转移