(N[2-PⁱPr₂-4-methylphenyl]₂)NbCl₃ | 919536-82-6

• 英文名称: (N[2-PⁱPr₂-4-methylphenyl]₂)NbCl₃
• 英文别名: NbCl3(N[2-P(iPr)2-4-methylphenyl]2)；(N[2-P(CHMe2)2-4-Me-C6H3]2)NbCl3
• CAS: 919536-82-6
• 化学式: C₂₆H₄₀Cl₃NNbP₂
• 分子量: 627.823
• InChiKey: OJMMJKVLTHMIBK-UHFFFAOYSA-K

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：

  (N[2-PⁱPr₂-4-methylphenyl]₂)NbCl₃ 、 Mg(CH2CMe3)2*99(dioxane) 以 甲苯 为溶剂， 生成 (N[2-P(CHMe2)2-4-Me-C6H3]2)Nb(=CHCMe3)2
  参考文献：
  名称：

  Niobium Bis-alkylidene Complexes Prepared by a Multi-Electron Redox Process

  摘要：

  High-valent niobium bis-alkylidene complexes have been structurally authenticated along with the first paramagnetic Nb(IV) alkylidene. The bis-alkylidene complexes presented in this work are thought to be generated via a redox process involving a-hydride elimination from a transient Nb(III) bis-alkyl complex. X-ray diffraction, DFT, and multinuclear NMR studies are consistent with these bis-alkylidenes having drastically different chemical environments.

  DOI：

  10.1021/om7008233
• 作为产物：
  描述：

  四氯双(四氢呋喃)合铌(IV) 、 Li[N(2-P(CHMe2)2-4-MeC6H3)2] 以 甲苯 为溶剂， 以69%的产率得到(N[2-PⁱPr₂-4-methylphenyl]₂)NbCl₃
  参考文献：
  名称：

  金属-配体协同作用组装中性和末端铌磷三键 (Nb≡P)

  摘要：

  磷原子从 [PCO] −转移到 Nb IV前体 [(PNP) NbCl 2 (N t BuAr)] (PNP=N[2-P i Pr 2 -4-methylphenyl] 2 − ; Ar=3,5- Me 2 C 6 H 3 ) 导致 P 原子脱羰和偶联，得到 [(PNPP)NbCl(N t BuAr)]。一个电子的还原在 Nb 上提供了第一个中性和末端磷配体，两个电子氧化重新形成了 P-P 键。进行了计算研究以了解这组转换中的机制。

  DOI：

  10.1002/anie.202212488

文献信息

• A Terminally Bound Niobium Methylidyne
  作者：Takashi Kurogi、Patrick J. Carroll、Daniel J. Mindiola

  DOI：10.1021/jacs.6b00830

  日期：2016.4.6

  example of a niobium methylidene, (PNP)Nb═CH2(OAr)(OTf), treatment of the dimethyl triflate precursor with the ylide H2CPPh3 produced the mononuclear group 5 methylidyne complex, (PNP)Nb≡CH(OAr). Adding a Brønsted base to (PNP)Nb═CH2(OAr)(OTf) also resulted in formation of the methylidyne. Solid-state structural analysis confirms both methylidene and methylidyne moieties to be terminal, having very short

  配合物 (PNP)Nb(CH3)2(OAr) (PNP = N[2-P(i)Pr2-4-methylphenyl]2(-), Ar = 2,6-(i)Pr2C6H3)，由处理(PNP)NbCl3 与 NaOAr 和 2 当量的 H3CMgCl，可以用 [FeCP2][OTf] 氧化得到 (PNP)Nb( )2(OAr)(OTf)。虽然后者的光解导致形成了一个罕见的亚甲基铌例子，(PNP)Nb=CH2(OAr)(OTf)，但用叶立德 H2CPPh3 处理三氟甲磺酸二甲酯前体产生了单核第 5 基亚甲基配合物，（PNP )Nb≡CH(OAr)。将布朗斯台德碱添加到 (PNP)Nb= (OAr)(OTf) 也导致形成亚甲基。固态结构分析证实亚甲基和亚甲基部分都是末端，具有非常短的 Nb-C 距离，分别为 1.963(2) 和 1.820(2) Å。
• Tellurolate: an effective Te-atom transfer reagent to prepare the triad of group 5 metal bis(tellurides)
  作者：Shuruthi Senthil、Seongyeon Kwon、Richard Y. Kong、Samantha N. MacMillan、Pavel Zatsepin、Michael R. Gau、Patrick J. Carroll、Mu-Hyun Baik、Kyle M. Lancaster、Daniel J. Mindiola

  DOI：10.1039/d3sc03470d

  日期：——

  show in this work how lithium tellurolate Li(X)nTeCH2SiMe3 (X = THF, n = 1, 1; X = 12-crown-4, n = 2, 2), can serve as an effective Te-atom transfer reagent to all group 5 transition metal halide precursors irrespective of the oxidation state. Mononuclear and bis(telluride) complexes, namely (PNP)M(Te)2 (M = V; Nb, 3; Ta, 4; PNP− = N[2-PiPr2-4-methylphenyl]2), are reported herein including structural

  我们在这项工作中展示了碲酸锂Li(X) n TeCH 2 SiMe 3 (X = THF, n = 1, 1 ; X = 12-冠-4, n = 2, 2 )如何作为有效的Te-原子转移试剂适用于所有第 5 族过渡金属卤化物前体，无论氧化态如何。单核和双（碲化物）配合物，即 (PNP)M(Te) 2 (M = V; Nb, 3 ; Ta, 4 ; PNP − = N[2-P i Pr 2 -4-甲基苯基] 2 )本文报道的包括结构和光谱数据。而已知的配合物 (PNP)V(Te) 2可以很容易地由三价前体 (PNP)VCl 2制备，两当量。碲酸盐和用PMe 3部分溶解的元素Te的络合物3也可以按照相同的程序类似地获得，但有或没有还原剂Na/NaCl。另一方面，复合物4是通过添加四个当量而形成的。碲酸盐转化为(PNP)TaF 4 。通过获取第 5 族金属的 (PNP)M(Te) 2系统三元组，我们可以结合理论和光谱（包括
• Activation of Atmospheric Nitrogen and Azobenzene NN Bond Cleavage by a Transient Nb(III) Complex
  作者：Uriah J. Kilgore、Xiaofan Yang、John Tomaszewski、John C. Huffman、Daniel J. Mindiola

  DOI：10.1021/ic061642b

  日期：2006.12.1

  Atmospheric N-2 is activated by two transient Nb(III) "(PNP) NbCl2"(PNP- = N[2-P(CHMe2)(2)-4-methylphenyl](2)) fragments to form the bridging diimido [(PNP)NbCl2]2(mu-N2) (1). Complex 1 can also be independently synthesized from Nb(IV) and Nb(V) precursors via one-electron and transmetalation reactions, respectively. In the presence of azobenzene, the transient Nb (III) intermediate, prepared from Li(PNP)and NbCl3(DME) (DME = dimethoxyethane) under Ar, cleaves the N=N bond via a metal-ligand cooperative four-electron reduction to form niobium imide and phosphoranimine functionalities. Structural studies are presented and discussed for various Nb systems bearing the pincer-type framework PNP as well as the N-2 and azobenzene activated products. Theoretical studies addressing the Nb-N-2-Nb core in 1 are also presented.