(bis(2-diisopropylphosphino-4-tolyl)amide)Sc(Cl2) | 1073683-73-4

• 英文名称: (bis(2-diisopropylphosphino-4-tolyl)amide)Sc(Cl2)
• 英文别名: (bis(2-diisopropylphosphino-4-tolyl)amide)Sc(Cl₂)；(N[2-PiPr2-4-methylphenyl]2)ScCl2；(PNP)Sc(Cl₂)；(PNP)ScCl2；[Sc(N[2-P(CHMe2)2-4-methylphenyl]2)Cl2]；(N[2-P(CHMe2)2-4-methylphenyl]2)ScCl2
• CAS: 1073683-73-4
• 化学式: C₂₆H₄₀Cl₂NP₂Sc
• 分子量: 544.42
• InChiKey: SEIPRZMXIDYWOC-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：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  (bis(2-diisopropylphosphino-4-tolyl)amide)Sc(Cl2) 生成 [Sc(N[2-P(CHMe2)2-4-methylphenyl]2)(CH2Si(CH3)3)(NHC6H3-iPr2-2,6)]
  参考文献：
  名称：

  存在末端亚氨基scan化合物的证据：分子间CH活化和与瞬时Sc = NAr物种的络合反应。

  摘要：

  DOI：

  10.1002/anie.200803325
• 作为产物：
  描述：

  [(N[2-P(CHMe2)2-4-methylphenyl]2)Sc(μ2-P-2,6-Mes2C6H3)(μ2-Br)Li] 、 2,4,6-tri-t-butylphenylphosphonous dichloride 以 not given 为溶剂， 生成 (bis(2-diisopropylphosphino-4-tolyl)amide)Sc(Cl2)
  参考文献：
  名称：

  Phosphinidene Complexes of Scandium: Powerful PAr Group-Transfer Vehicles to Organic and Inorganic Substrates

  摘要：

  The first phosphinidene complexes of scandium are reported in this contribution. When complex (PNP)Sc(CH3)Br (1) is treated with 1 equiv of LiPH[Trip] (Trip = 2,4,6-(Pr3C6H2)-Pr-i), the dinuclear scandium phosphinidene complex [(PNP)Sc(mu(2)-P[Trip])](2) (2) is obtained. However, treating 1 with a bulkier primary phosphide produces the mononuclear scandium ate complex [(PNP)Sc(mu(2)-P[DMP](mu(2)-Br)Li] (3) (DMP = 2,6-Mes(2)C(6)H(3)). The Li cation in 3 can be partially encapsulated with DME to furnish a phosphinidene salt derivative, (PNP)Sc(mu(2)-P[DMP])(mu(2)-Br)Li(DME)] (4). We also demonstrate that complex 3 can readily deliver the phosphinidene ligand to organic substrates such as OCPh2 and Cl(2)PMes* as well as inorganic fragments such as Cp2ZrCl2, Cp*2TiCl2, and Cp2TiCl2 in the presence of P(CH3)(3). Complexes 2-4 have been fully characterized, including single crystal X-ray diffraction and DFT Studies.

  DOI：

  10.1021/ja100214e

文献信息

• Tebbe-like and Phosphonioalkylidene and -alkylidyne Complexes of Scandium
  作者：Pavel Zatsepin、Eunji Lee、Jun Gu、Michael R. Gau、Patrick J. Carroll、Mu-Hyun Baik、Daniel J. Mindiola

  DOI：10.1021/jacs.0c02742

  日期：2020.6.3

  The bonding between scandium and carbon in a series of alkylidene and alkylidyne-like moieties is compared. The Tebbe-analogue complex (PNP)Sc(μ2-CHSiMe3)(μ2-CH3)[Al(CH3)(CH2SiMe3)] (2) (PNP- = N[2-PiPr2-4-methylphenyl]2), could be formed by adding AlMe3 to (PNP)Sc(CH2SiMe3)2 (1). The fluxional behavior of 2 is stud-ied by a combination of 2D 13C-1H HMQC, HMBC and other heteronuclear NMR spectroscopic

  比较了一系列亚烷基和亚烷基类部分中钪和碳之间的键合。Tebbe-类似物复合物 (PNP)Sc(μ2-CHSiMe3)(μ2-CH3)[Al( )(CH2SiMe3)] (2) (PNP- = N[2-PiPr2-4-methylphenyl]2)，可以是通过将 AlMe3 添加到 (PNP)Sc(CH2SiMe3)2 (1) 中形成。通过2D 13C-1H HMQC、HMBC和其他异核NMR光谱实验的组合研究了2的通量行为。膦酰亚烷基配合物 (PNP)Sc(CHPPh3)( ) (3) 可以通过用 2 当量的叶立德 H2CPPh3 处理或通过从 (PNP)Sc( )2 和一当量的 H2CPPh3 中消除甲烷来制备. 用 N3Ad 进一步探索了 2 中亚烷基的反应性，这在 Sc-C 键处插入，产生 (PNP)Sc( )[η2-N3AdCHSiMe3Al( )(CH2SiMe3)]
• 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
• Lewis Acid Stabilized Methylidene and Oxoscandium Complexes
  作者：Jennifer Scott、Hongjun Fan、Benjamin F. Wicker、Alison R. Fout、Mu-Hyun Baik、Daniel J. Mindiola

  DOI：10.1021/ja806635x

  日期：2008.11.5

  The methylidene scandium complex (PNP)Sc(mu(3)-CH2)(mu(2)-CH3)(2)[Al(CH3)(2)](2) (PNP=N[2-P(CHMe2)2-4-methylpheyl](2)(-)) can be prepared from the reaction of (PNP)Sc(CH3)(2) and 2 equiv of Al(CH3)(3). The Lewis acid stabilized methylidenes candium complex has been crystallographically characterized, and its bonding scheme analyzed by DFT. In addition, we report preliminary reactivity studies of the Sc-CH2 ligand with substrates such as H2NAr and OCPh2. While the former results in an Bronsted acid-base reaction, the latter reagent produces the olefin H2C-CPh2 along with the novel oxoscandium complex (PNP)Sc(mu(3)-O)(mu(2)-CH3)(2)[Al(CH3)(2)](2), quantitatively.