[Zn{C(3,5-dimethylpyrazolyl)3}{N(SiMe3)2}] | 1215113-02-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并三唑类
• 英文名称: [Zn{C(3,5-dimethylpyrazolyl)3}{N(SiMe3)2}]
• 英文别名: [Zn{C(3,5-dimethylpyrazolyl)₃}{N(SiMe₃)₂}]；[Zn{C(3,5-Me₂pz)₃}{N(SiMe₃)₂}]；Zn(tris(3,5-dimethylpyrazolyl)methanide)(N(SiMe3)2)
• CAS: 1215113-02-2
• 化学式: C₂₂H₃₉N₇Si₂Zn
• 分子量: 523.16
• InChiKey: CICUIQPDLMAAMJ-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：
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• 拓扑面积：
  None
• 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：

  [Zn{C(3,5-dimethylpyrazolyl)3}{N(SiMe3)2}] 、 三(3,5-二甲基-1-吡唑基)甲烷 以 氘代苯 为溶剂， 以0%的产率得到Zn(tris(3,5-dimethylpyrazolyl)methanide)2
  参考文献：
  名称：

  Syntheses and Structural Diversity of Group 2 and Group 12 Tris(pyrazolyl)methaneand Zwitterionic Tris(pyrazolyl)methanideCompounds

  摘要：

  Reaction of HC(Me(2)pz)(3) with Mg{N(SiMe3)(2)}(2) gave the zwitterionic amide complex Mg{C(Me(2)pz)(3)}{N(SiMe3)(2)} (13), containing a free pyramidal carbanion and a cationic {Mg-N(SiMe3)(2)}(+) moiety. Reaction of the less bulky amide Mg{N(SiHMe2)(2)}(2) with RC(Me(2)pz)(3) (R = H or D) gave the four-coordinate adducts Mg{kappa N-2-RC(Me(2)pz)(3)}{N(SiHMe2)(2)}(2) (R = H (15) or D (15-d)). A similar complex, Mg{kappa N-2-HC(Me(2)pz)(3)}{N(SiMe3)(2)}(2) (14), was observed by NMR spectroscopy at low temperatures. On warming, 15, 15-d, and 14 eliminated RN(SiR'Me-2)(2) (R' = H or Me) to form Mg{C(Me(2)pz)(3)}{N(SiR'Me-2)(2)} (13 or 17). The reactions of 15 and 15-d followed first-order kinetics with a primary kinetic isotope effect (k(H)/k(D)) of 1.91(2). Reaction of 13 or 17 with a further equivalent of HC(Me(2)pz)(3) gave the homoleptic sandwich complex Mg{C(Me(2)pz)(3)}(2) (previously reported), containing two free carbanions and a dicationic metal center. The reaction of 17 with an excess of RC(Me(2)pz)(3) (R = H or D) followed pseudo-first-order kinetics with a primary kinetic isotope effect of 1.51(4). The corresponding reactions of Ca{N(SiMe3)(2)}(2)(THF)(2) with 1 or 2 equiv of HC(Me(2)pz)(3) gave Ca{C(Me(2)pz)(3)}{N(SiMe3)(2)}(THF) (18) or Ca{C(Me(2)pz)(3)}(2) (19). In contrast, Zn{N(SiMe3)(2)}(2) was effectively unreactive toward HC(Me(2)pz)(3). However, reaction of ZnCl2 with 1 or 2 equiv of Li{C(Me(2)pz)(3)}(THF) afforded Zn{C(Me(2)pz)(3)}Cl (20) or Zn{C(Me(2)pz)(3)}(2) (23), respectively. Subsequent reaction of 20 with NaN(SiMe3)(2) or LiN(SiHMe2)(2) formed Zn{C(Me(2)pz)(3)}{N(SiRMe2)(2)} (R = Me (21) or H). Cd{N(SiMe3)(2)}(2) reacted with 1 or 2 equiv of HC(Me(2)pz)(3) to form Cd{C(Me(2)pz)(3)}{N(SiMe3)(2)} (24) or Cd{C(Me(2)pz)(3)}(2) (25). Reaction of 13 or 18 with HC(pz)(3) gave the heteroleptic zwitterions M{C(Me(2)pz)(3)}{C(pz)(3)} (M = Mg (26) or Ca (27)), containing kappa N-3-coordinated C(Me(2)pz)(3) and C(pz)(3) ligands. In contrast, reaction of 24 with HC(pz)(3) formed Cd{C(Me(2)pz)(3)}{kappa C-1, kappa N-2-C(pz)(3)} (28), containing two different coordination modes for the tris(pyrazolyl)methanide ligands and a Cd-C(pz)(3) bond. The solid-state structures of 13, 15, 18, 19, 20, 21, 23, 24, 26, and 28 have been determined.

  DOI：

  10.1021/om901013b
• 作为产物：
  描述：

  [Li(tris(3,5-dimethylpyrazolyl)methanido)(thf)] 以 四氢呋喃 、 乙醚 、 苯 为溶剂， 生成 [Zn{C(3,5-dimethylpyrazolyl)3}{N(SiMe3)2}]
  参考文献：
  名称：

  Syntheses and Structural Diversity of Group 2 and Group 12 Tris(pyrazolyl)methaneand Zwitterionic Tris(pyrazolyl)methanideCompounds

  摘要：

  Reaction of HC(Me(2)pz)(3) with Mg{N(SiMe3)(2)}(2) gave the zwitterionic amide complex Mg{C(Me(2)pz)(3)}{N(SiMe3)(2)} (13), containing a free pyramidal carbanion and a cationic {Mg-N(SiMe3)(2)}(+) moiety. Reaction of the less bulky amide Mg{N(SiHMe2)(2)}(2) with RC(Me(2)pz)(3) (R = H or D) gave the four-coordinate adducts Mg{kappa N-2-RC(Me(2)pz)(3)}{N(SiHMe2)(2)}(2) (R = H (15) or D (15-d)). A similar complex, Mg{kappa N-2-HC(Me(2)pz)(3)}{N(SiMe3)(2)}(2) (14), was observed by NMR spectroscopy at low temperatures. On warming, 15, 15-d, and 14 eliminated RN(SiR'Me-2)(2) (R' = H or Me) to form Mg{C(Me(2)pz)(3)}{N(SiR'Me-2)(2)} (13 or 17). The reactions of 15 and 15-d followed first-order kinetics with a primary kinetic isotope effect (k(H)/k(D)) of 1.91(2). Reaction of 13 or 17 with a further equivalent of HC(Me(2)pz)(3) gave the homoleptic sandwich complex Mg{C(Me(2)pz)(3)}(2) (previously reported), containing two free carbanions and a dicationic metal center. The reaction of 17 with an excess of RC(Me(2)pz)(3) (R = H or D) followed pseudo-first-order kinetics with a primary kinetic isotope effect of 1.51(4). The corresponding reactions of Ca{N(SiMe3)(2)}(2)(THF)(2) with 1 or 2 equiv of HC(Me(2)pz)(3) gave Ca{C(Me(2)pz)(3)}{N(SiMe3)(2)}(THF) (18) or Ca{C(Me(2)pz)(3)}(2) (19). In contrast, Zn{N(SiMe3)(2)}(2) was effectively unreactive toward HC(Me(2)pz)(3). However, reaction of ZnCl2 with 1 or 2 equiv of Li{C(Me(2)pz)(3)}(THF) afforded Zn{C(Me(2)pz)(3)}Cl (20) or Zn{C(Me(2)pz)(3)}(2) (23), respectively. Subsequent reaction of 20 with NaN(SiMe3)(2) or LiN(SiHMe2)(2) formed Zn{C(Me(2)pz)(3)}{N(SiRMe2)(2)} (R = Me (21) or H). Cd{N(SiMe3)(2)}(2) reacted with 1 or 2 equiv of HC(Me(2)pz)(3) to form Cd{C(Me(2)pz)(3)}{N(SiMe3)(2)} (24) or Cd{C(Me(2)pz)(3)}(2) (25). Reaction of 13 or 18 with HC(pz)(3) gave the heteroleptic zwitterions M{C(Me(2)pz)(3)}{C(pz)(3)} (M = Mg (26) or Ca (27)), containing kappa N-3-coordinated C(Me(2)pz)(3) and C(pz)(3) ligands. In contrast, reaction of 24 with HC(pz)(3) formed Cd{C(Me(2)pz)(3)}{kappa C-1, kappa N-2-C(pz)(3)} (28), containing two different coordination modes for the tris(pyrazolyl)methanide ligands and a Cd-C(pz)(3) bond. The solid-state structures of 13, 15, 18, 19, 20, 21, 23, 24, 26, and 28 have been determined.

  DOI：

  10.1021/om901013b

文献信息

• Tris(3,5-dimethylpyrazolyl)methane-Based Heterobimetallic Complexes that Contain Zn and CdTransition-Metal Bonds: Synthesis, Structures, and Quantum Chemical Calculations
  作者：Jens Meyer、Sandra González-Gallardo、Silvia Hohnstein、Delphine Garnier、Markus K. Armbruster、Karin Fink、Wim Klopper、Frank Breher

  DOI：10.1002/chem.201405397

  日期：2015.2.9

  conversion of the tris(3,5‐dimethylpyrazolyl)methanide ligand (Tpmd*) into the ‐methane derivative (Tpm*) and the reaction of the acidic hydride MH bond with the M′N(SiMe3)2 moiety. The latter produces HN(SiMe3)2 as a byproduct. The Group 2 representatives [Mg(Tpm*)MCp(CO)3}2(thf)] (3 a/b) form isocarbonyl bridges between the magnesium and chromium/molybdenum centres, whereas direct metal–metal bonds are

  三（3,5-二甲基吡唑基）甲酰胺酰胺配合物[M'C（3,5-Me 2 pz）3 } N（SiMe 3）2 }]的反应（M'= Mg（1 a），Zn （1 b），Cd（1 c）； 3,5-Me 2 pz = 3,5-二甲基吡唑基）和两个当量的酸性6环戊二烯基（Cp）三羰基氢化物[MCp（CO）3 H]（M = Cr（2 a），Mo（2 b））给出了不同类型的异双金属配合物。在每种情况下，两个反应发生后，三即转换（3,5-二甲基）甲烷化配体（TPMD *）进入-甲烷衍生物（TPM *）和酸性氢化物M的反应H键与M'N（SiMe 3）2部分结合。后者产生HN（SiMe 3）2作为副产物。第2组代表[Mg（TPM *）MCp（CO）3 } 2（thf）]（3 a / b）在镁和铬/钼中心之间形成异羰基桥，而在离子[Zn（TPM *）MCp（CO）3 }] +（4 a / b； [MCp（CO）3