(bis(2-diisopropylphosphino-4-tolyl)amide)Sc(NH[2,6-diisopropylphenyl])(η2-NC5H4) | 1095281-58-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (bis(2-diisopropylphosphino-4-tolyl)amide)Sc(NH[2,6-diisopropylphenyl])(η2-NC5H4)
• 英文别名: (bis(2-diisopropylphosphino-4-tolyl)amide)Sc(NH[2,6-diisopropylphenyl])(η²-NC₅H₄)；(PNP)Sc(NH[DIPP])(η²-NC₅H₄)；[(N(C6H3-4-Me-2-P(CHMe2)2)2)Sc(NH(2,6-iPr2C6H3))(η2-pyridyl)]；[(N(C6H3-4-Me-2-P(iPr)2)2)Sc(NHDipp)(η2-C5H4N)]；[(N(C6H3(CH3)P(iPr)2)2)Sc(NH(DIPP))(η2-pyridyl)]；[(N(C6H3-4-CH3-2-P(iPr)2)2)Sc(NH(2,6-iPr2C6H3))(η2-pyridyl)]
• CAS: 1095281-58-5
• 化学式: C₄₃H₆₂N₃P₂Sc
• 分子量: 727.889
• InChiKey: IHQPHDSCRDVENI-UHFFFAOYSA-N

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：

  (bis(2-diisopropylphosphino-4-tolyl)amide)Sc(NH[2,6-diisopropylphenyl])(η2-NC5H4) 以 not given 为溶剂， 生成 [(N(C6H3-4-Me-2-P(iPr)2)2)Sc(NHDipp)(η2-(DMeP)NC(C5H3N)CHN(DIPP))]
  参考文献：
  名称：

  Atom-Economical Route to Substituted Pyridines via a Scandium Imide

  摘要：

  Taking advantage of a tautomerization process between (PNP)Sc=N(DIPP)(NC5H5) (PNP = N[2-P(CHMe2)(2)-4-methylphenyl](2)(-), DIPP = 2,6-iPr(2)C(6)H(3)) and (PNP)Sc(NH-(DIPP))(eta(2)-NC5H4) (1), we demonstrate in this work that pyridine can be both activated and functionalized with isonitriles (in one case catalytically) to ultimately afford mono- and bis-imino-substituted pyridines. Several intermediates in the cycle have been isolated and characterized.

  DOI：

  10.1021/om2001537
• 作为产物：
  描述：

  吡啶 、 [(N(C6H3-4-Me-2-P(iPr)2)2)Sc(NHDipp)((DIPP)NC(C5H4N))] 以 not given 为溶剂， 生成 (bis(2-diisopropylphosphino-4-tolyl)amide)Sc(NH[2,6-diisopropylphenyl])(η2-NC5H4)
  参考文献：
  名称：

  Atom-Economical Route to Substituted Pyridines via a Scandium Imide

  摘要：

  Taking advantage of a tautomerization process between (PNP)Sc=N(DIPP)(NC5H5) (PNP = N[2-P(CHMe2)(2)-4-methylphenyl](2)(-), DIPP = 2,6-iPr(2)C(6)H(3)) and (PNP)Sc(NH-(DIPP))(eta(2)-NC5H4) (1), we demonstrate in this work that pyridine can be both activated and functionalized with isonitriles (in one case catalytically) to ultimately afford mono- and bis-imino-substituted pyridines. Several intermediates in the cycle have been isolated and characterized.

  DOI：

  10.1021/om2001537

文献信息

• Isocyanide insertion and cyclization reactions to form indolines using pincer-type complexes of scandium
  作者：Benjamin F. Wicker、Maren Pink、Daniel J. Mindiola

  DOI：10.1039/c1dt10287g

  日期：——

  The addition of 2,6-dimethylphenyl isocyanide (CN[DMeP], two equivalents) to previously reported (PNP)Sc(III) pyridyl complexes resulted in the formation of novel indoline complexes of scandium. By varying the nature of the pyridyl moiety one can intercept an intermediate prior to methyl migration. In addition to structural studies of two indolene complexes, we also propose a mechanism for the insertion and indolene ring closure.

  将 2,6-二甲基苯基异氰酸酯（CN[DMeP]，两个等价物）添加到之前报道的 (PNP)Sc(III) 吡啶络合物中，可形成新型的钪吲哚啉络合物。通过改变吡啶基的性质，可以在甲基迁移之前截取一个中间体。除了对两种吲哚啉配合物进行结构研究外，我们还提出了插入和吲哚啉环闭合的机理。
• Evidence for the Existence of Terminal Scandium Imidos: Mechanistic Studies Involving Imido–Scandium Bond Formation and C–H Activation Reactions
  作者：Benjamin F. Wicker、Hongjun Fan、Anne K. Hickey、Marco G. Crestani、Jennifer Scott、Maren Pink、Daniel J. Mindiola

  DOI：10.1021/ja307279r

  日期：2012.12.12

  presence of pyridine to generate the transient scandium imido (PNP)Sc═N[DIPP](NC(5)H(5)) (A-py), which rapidly activates the C-H bond of pyridine in 1,2-addition fashion to form the stable pyridyl complex (PNP)Sc(NH[DIPP])(η(2)-NC(5)H(4)) (2). Mechanistic studies suggest the C-H activation process to be second order overall: first order in scandium and first order in substrate (pyridine). Pyridine binding

  苯胺-甲基复合物 (PNP)Sc(NH[DIPP])(CH(3)) (1) [PNP(-) = 双(2-二异丙基膦基-4-甲苯基)酰胺，DIPP = 2,6-二异丙基苯基]在吡啶存在下消除甲烷（k(avg) = 5.13 × 10(-4) M(-1) s(-1) at 50 °C）以生成瞬态亚氨基钪 (PNP)Sc=N[DIPP] (NC(5)H(5)) (A-py)，以 1,2-加成方式快速激活吡啶的 CH 键，形成稳定的吡啶基络合物 (PNP)Sc(NH[DIPP])(η( 2)-NC(5)H(4)) (2)。机理研究表明 CH 活化过程总体上是二阶的：一阶在钪中，一阶在底物（吡啶）中。吡啶结合先于甲烷的消除，并且 α-氢提取是总体速率决定性的 [1-d(1) 转化为 2 的动力学同位素效应 (KIE) 在 35 °C 和 4.9(14) 时为 5.37(6)在 50 °C] 激活参数