[iPrNC(CH3)NPri]2ZrCl2 | 1448043-12-6

• 英文名称: [iPrNC(CH3)NPri]2ZrCl2
• 英文别名: [ⁱPrNC(CH₃)NPrⁱ]₂ZrCl₂；Zr[MeC(NⁱPr)₂]₂Cl₂
• CAS: 1448043-12-6
• 化学式: C₁₆H₃₄Cl₂N₄Zr
• 分子量: 444.603
• InChiKey: KIULFESXFGCWEX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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：

  [iPrNC(CH3)NPri]2ZrCl2 、 lithium dimethylamide 以22%的产率得到Zr(NMe₂)₂[MeC(NⁱPr)₂]₂
  参考文献：
  名称：

  Preparation of all N-coordinated zirconium amide amidinates and studies of their reactions with dioxygen and water

  摘要：

  Zr(NR2)(2)[MeC((NPr)-Pr-i)(2)](2) (R = Me, 1; Et, 2) have been prepared through aminolysis and their reactions with O-2 and water have been studied. Two major products from the reactions are the oxo dimer {(mu-O)Zr[MeC((NPr)-Pr-i)(2)](2))(2) (3) and its insoluble polymer {(mu-O)Zr[MeC((NPr)-Pr-i)(2)](2)}(n) (4). Over time the dimer 3 polymerizes to 4. Zr peroxo trimer {(mu-eta(2):eta(2)-O-2)Zr[MeC((NPr)-Pr-i)(2)](2)}(3) (5) was also observed from the reaction of 1 with O-2 and its crystal structure is reported. DFT calculations show that the reaction of 1 with O-2 follows a radical process, yielding the peroxo trimer 5. Mass spectrometric studies of the reactions of water in air with 1 and 2 show the formation of the oxo monomer (O=)Zr[MeC((NPr)-Pr-i)(2)](2) (6), oxo dimer {(mu-O)Zr[MeC((NPr)-Pr-i)(2)](2)}(2).(3), and the dihydroxy monomer (HO)(2)Zr[MeC((NPr)-Pr-i)(2)](2) (7). In addition, the cations (Zr(NR2)[MeC((NPr)-Pr-i)(2)](2)}(+) (R = Me, Et) Were observed. 2 revealed an interesting dynamic NMR behavior. Variable-temperature (VT) NMR spectroscopy has been used to study the Bailar twist process in 2, giving activation parameters Delta H-double dagger = 10.9(1.1) kcal mol(-1), Delta S-double dagger = -11(4) eu and Delta G(303 kappa)(double dagger) = 14(2) kcal mol(-1). (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2015.07.045
• 作为产物：
  描述：

  lithium N,N'-diisopropylacetamidinate 、 氯化锆(IV) 以 正己烷 为溶剂， 反应 6.0h， 以68.5%的产率得到[iPrNC(CH3)NPri]2ZrCl2
  参考文献：
  名称：

  Preparation of all N-coordinated zirconium amide amidinates and studies of their reactions with dioxygen and water

  摘要：

  Zr(NR2)(2)[MeC((NPr)-Pr-i)(2)](2) (R = Me, 1; Et, 2) have been prepared through aminolysis and their reactions with O-2 and water have been studied. Two major products from the reactions are the oxo dimer {(mu-O)Zr[MeC((NPr)-Pr-i)(2)](2))(2) (3) and its insoluble polymer {(mu-O)Zr[MeC((NPr)-Pr-i)(2)](2)}(n) (4). Over time the dimer 3 polymerizes to 4. Zr peroxo trimer {(mu-eta(2):eta(2)-O-2)Zr[MeC((NPr)-Pr-i)(2)](2)}(3) (5) was also observed from the reaction of 1 with O-2 and its crystal structure is reported. DFT calculations show that the reaction of 1 with O-2 follows a radical process, yielding the peroxo trimer 5. Mass spectrometric studies of the reactions of water in air with 1 and 2 show the formation of the oxo monomer (O=)Zr[MeC((NPr)-Pr-i)(2)](2) (6), oxo dimer {(mu-O)Zr[MeC((NPr)-Pr-i)(2)](2)}(2).(3), and the dihydroxy monomer (HO)(2)Zr[MeC((NPr)-Pr-i)(2)](2) (7). In addition, the cations (Zr(NR2)[MeC((NPr)-Pr-i)(2)](2)}(+) (R = Me, Et) Were observed. 2 revealed an interesting dynamic NMR behavior. Variable-temperature (VT) NMR spectroscopy has been used to study the Bailar twist process in 2, giving activation parameters Delta H-double dagger = 10.9(1.1) kcal mol(-1), Delta S-double dagger = -11(4) eu and Delta G(303 kappa)(double dagger) = 14(2) kcal mol(-1). (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2015.07.045

文献信息

• Synthesis of Neutral Group 4 Metal–Carboryne Complexes and Their Reactivity toward Unsaturated Molecules
  作者：Shikuo Ren、Zaozao Qiu、Zuowei Xie

  DOI：10.1021/om400458r

  日期：2013.8.12

  thioisocyanate, carbon disulfide, and phenyl azide to give various monoinsertion products, in which the unsaturated bond inserted into one of the M–Ccage bonds, resulting in the formation of heterocycles. However, these metal–carboryne complexes did not show any reactivity toward pyridines, alkynes, and alkenes. The results clearly indicated that [η2-R2C(NR1)2]2M(η2-C2B10H10) shared some common properties with Cp2Zr(η2-C2B10H10)

  一系列中性组4的一般类型的金属- carboryne络合物[η 2 -R 2 C（NR 1）2 ] 2 M（η 2 -C 2乙10 ħ 10）经[η的复分解反应制备2 -R 2 C（NR 1）2 ] 2 MCl 2和Li 2 C 2 B 10 H 10（M = Ti，Zr，Hf; R 1 = i Pr，环己基，R 2 = Me，nBu，Ph）高产。通过单晶X射线分析证实了它们的结构。它们与酮，腈和杂多烯（如碳二亚胺，异氰酸酯，硫代异氰酸酯，二硫化碳和叠氮化苯）反应生成各种单插入产物，其中不饱和键插入到一个MC笼键中，从而形成杂环。但是，这些金属-碳炔复合物对吡啶，炔烃和烯烃没有任何反应性。结果清楚地表明，[η 2 -R 2 C（NR 1）2 ] 2 M（η 2 -C 2乙10 ħ 10）共享再用Cp一些常见的性质2的Zr（η 2 -C 2乙10 ħ 10与heterocumulenes反应）;