[Li(N,N′-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)(THF)] | 930287-20-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: [Li(N,N′-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)(THF)]
• 英文别名: [Li(pbpamd)(THF)]；Li(κ³-N,N'-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)(tetrahydrofuran)；Li(κ³-pbpamd)(thf)；[Li(N,N'-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)(THF)]；Li(THF)(κ3-N,N'-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)；Li(THF)(κ3-pbpamd)；lithium;[C-[bis(3,5-dimethylpyrazol-1-yl)methyl]-N-propan-2-ylcarbonimidoyl]-propan-2-ylazanide;oxolane
• CAS: 930287-20-0
• 化学式: C₂₂H₃₇LiN₆O
• 分子量: 408.516
• InChiKey: OAQSCGCJEQJKOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.75
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  58.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [Li(N,N′-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)(THF)] 在 Li(CH₂)3CH₃ 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 Zn(NH-4-MeC6H4)(N,N'-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)
  参考文献：
  名称：

  a基杂蝎子配体支持的新型氯化锌和酰胺配合物的合成，结构和开环聚合研究。

  摘要：

  异蝎子锂盐[Li（pbpamd）（THF）] [pbpamd = N，N'-二异丙基双（3,5-二甲基吡唑-1-基）乙酰胺酸盐]和[Li（tbpamd）（THF）] [tbpamd =含1当量ZnCl2的N-乙基-N'-叔丁基双（3,5-二甲基吡唑-1-基）乙酰胺酸酯]提供了非常高产率的中性杂蝎子酸盐氯化锌配合物[ZnCl（NNN）]（NNN = pbpamd 1和tbpamd 2）。化合物1用作合成芳族酰胺锌化合物[Zn（NHAr）（pbpamd）]的方便原料，其中NHAr = 4-甲基苯基酰胺（NH-4-MeC6H4）3，2,4,6-三甲基苯基酰胺（ NH-2,4,6-Me3C6H2）4和2,6-二乙基苯基酰胺（NH-2,6-Et2C6H3）5通过相应的芳族伯酰胺锂盐反应而生成。另外，脂肪族酰胺衍生物[Zn（NR2）（pbpamd）]（R = SiMe3 6，SiHMe2 7和iPr

  DOI：

  10.1039/b910048b
• 作为产物：
  描述：

  四氢呋喃 、 正丁基锂 、 1-[(3,5-二甲基吡唑-1-基)甲基]-3,5-二甲基吡唑 、 N,N'-二异丙基碳二亚胺 生成 [Li(N,N′-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)(THF)]
  参考文献：
  名称：

  多核异丁基镁叔丁基镁的研究：外消旋丙交酯的合成，配位能力和杂环选择性开环聚合

  摘要：

  The reaction of the low sterically hindered heteroscorpionate lithium acetamidinates [Li(kappa(3)-NNN)(thf)] {NNN = pbpamd (1) [pbpamd = N,N'-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate], tbpamd (2) [tbpamd = N-ethyl-N'-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate], ttbpamd (3) [ttbpamd = N,N'-di-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate], phbpamd (4) [phbpamd = N,N'-di-p-tolylbis(3,5-dimethylpyrazol-1-yl)acetamidinate] and the highly sterically demanding [Li(kappa(3)-phbptamd)(thf)] (5) [phbp(t)amd = N,N'-di-p-tolylbis(3,5-di-tert-butylpyrazol-1-yl)acetamidinate] with the commercially available Grignard reagent (BuMgCl)-Bu-t in an equimolecular ratio yielded the magnesium tert-butyl heteroscorpionates [Mg(Bu-t)(kappa(3)-NNN)] [NNN = pbpamd (6), tbpamd (7), ttbpamd (8), and phbptamd (9)]. In addition, subsequent reaction of monoalkyls 6-8 with two additional equivalents of (BuMgCl)-Bu-t gave rise to two different classes of chiral tetraalkyls, which contain apical methine C-H activated heteroscorpionates that show two possible coordination modes, namely, the tetranuclear complexes [{(Bu-t)Mg(kappa(3)-N,N,N;kappa(2)-C,N)Mg(Bu-t)}(2){-O,O-(OC4H8O)}] (kappa(3)-N,N,N;kappa(2)-C,N = pbpamd 10, tbpamd 11a) and [(Bu-t)Mg(kappa(2)-N,N;kappa(2)-N,N)Mg(Bu-t){-O,O-(OC4H8O)}](2) (kappa(2)-N,N;kappa(2)-N,N = tbpamd 11b). This reaction for 8 was unsuccessful, but an analog such as dinuclear complex [(thf)(Bu-t)Mg(kappa(2)-N,N;kappa(2)-N,N)Mg(Bu-t)(thf)] (kappa(2)-N,N;kappa(2)-N,N = phbpamd 12) could be obtained from its lithium salt. Contrary to complexes 10-12, the C-H activation process was not observed for complex 9, but interestingly, the coordination of one additional equivalent of MgtBu2 afforded dinuclear complex [Mg(Bu-t)(kappa(3)-phbptamd){Mg(Bu-t)(2)}] (13). Similarly, coordination of MgtBu(2) to 10 produces chiral trinuclear [{(Bu-t)Mg(pbpamd(-))Mg(tBu)}{-O,O-(OC4H8O)}{Mg(Bu-t)(2)(thf)}] (14). The X-ray crystal structures of complexes 4, 6, 8, 9, 11b, 12, 13, and 14 confirm the nuclearity of each family, and the existence of apical sigma-C(sp(3))-Mg (14) and extended pi-C2N2(sp(2))-Mg-2 (11b and 12) covalent bonds have unambiguously been also confirmed. Furthermore, mononuclear compounds 8 and 9, tetranuclear compound 10, and dinuclear compounds 12 and 13 can act as highly efficient single-component living initiators for the ring-opening polymerization of rac-lactide. More interestingly, the most sterically hindered initiators exhibit enhanced levels of heteroselectivity on the PLAs, with 9 reaching Ps values up to 0.85.

  DOI：

  10.1021/acs.organomet.6b00934

文献信息

• Heteroscorpionate Magnesium Alkyls Bearing Unprecedented Apical σ-C(sp³)–Mg Bonds: Heteroselective Ring-Opening Polymerization of <i>rac</i>-Lactide
  作者：Andrés Garcés、Luis F. Sánchez-Barba、Juan Fernández-Baeza、Antonio Otero、Manuel Honrado、Agustín Lara-Sánchez、Ana M. Rodríguez

  DOI：10.1021/ic401915b

  日期：2013.11.4

  and lactides. Lactide (LA) polymerizations afforded polylactide (PLA) materials with medium molecular weights in only a few minutes even at 20 °C for l-LA and in a few hours at 50 °C for rac-LA propagations. More importantly, microstructural analysis of the poly(rac-lactide) materials revealed that the tetranuclear tetra-alkyl 12 exerts enhanced levels of heteroselectivity on the PLAs under mild conditions

  低的前述反应的空间位阻heteroscorpionate锂acetamidinates [李（κ 3 -pbpamd）（THF）]和[李（κ 3 -tbpamd）（THF）〕与一系列可商购的格利雅的在等比试剂RMgCl纯化，产生镁monoalkyls [Mg的（R）（κ 3 -NNN）]（NNN = pbpamd，R = CH 2森达3，的Et（1），BN（2）; NNN = tbpamd，R = CH 2森达3，等（3），Bn（4））。然而，这些monoalkyls的后续反应[Mg的（R）（κ 3-NNN）]用相同RMgCl的两个额外当量的在四氢呋喃中引起了类型[RMG的双核二烷基（κ 3 - Ñ，Ñ，Ñ ;κ 2 -C，Ñ）MGR（THF）]（κ 3 - ñ，ñ，ñ ;κ 2 -C，ñ = pbpamd -，R = CH 2森达3（5），等（6）;κ 3 - ñ，ñ，ñ ;κ 2 -C，ñ＝
• Lithium, Titanium, and Zirconium Complexes with Novel Amidinate Scorpionate Ligands
  作者：Antonio Otero、Juan Fernández-Baeza、Antonio Antiñolo、Juan Tejeda、Agustín Lara-Sánchez、Luis F. Sánchez-Barba、Isabel López-Solera、Ana M. Rodríguez

  DOI：10.1021/ic062093c

  日期：2007.3.1

  form of the lithium derivatives [Li(NNN)(THF)] (NNN = pbpamd (1) (pbpamd = N,N'-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate); cbpamd (2) (cbpamd = N,N'-dicyclohexylbis(3,5-dimethylpyrazol-1-yl)acetamidinate); and tbpamd (3) (tbpamd = N-ethyl-N'-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)), although a similar process with N,N'-dimethylcarbodiimide gave the dinuclear complex [Li(bpzii)(THF)]2

  双（3,5-二甲基吡唑-1-基）甲烷（bdmpzm）与BunLi和碳二亚胺衍生物（N，N'-二异丙基，二环己基和1-叔丁基-3-乙基碳二亚胺）反应锂衍生物[Li（NNN）（THF）]形式的新杂蝎子配体的制备（NNN = pbpamd（1）（pbpamd = N，N'-二异丙基双（3,5-二甲基吡唑-1-基）乙酰胺酸酯） ； cbpamd（2）（cbpamd = N，N'-二环己基双（3,5-二甲基吡唑-1-基）乙酰胺酸酯）；和tbpamd（3）（tbpamd = N-乙基-N'-叔丁基双（3,5 -二甲基吡唑-1-基）乙酰胺酸酯）），尽管用N，N'-二甲基碳二亚胺进行类似的反应得到了双核络合物[Li（bpzii）（THF）] 2（4）（bpzii = N-（二甲基氨基）-N' -[[（二甲基氨基）双（3，5-二甲基吡唑-1-基）甲基亚氨基]亚胺基）。当最后的反应在空气中进行时，簇复合物[L