lithium N,N'-di(propan-2-yl)-n-butylamidinate

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: lithium N,N'-di(propan-2-yl)-n-butylamidinate
• 英文别名: Li[nBuC(N(iPr))2]；Li[(iPrN)2CnBu]；lithium;(C-butyl-N-propan-2-ylcarbonimidoyl)-propan-2-ylazanide
• 化学式: C₁₁H₂₃N₂*Li
• 分子量: 190.258
• InChiKey: BTJQNZAZINQRRF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.77
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  13.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  lithium N,N'-di(propan-2-yl)-n-butylamidinate 、 三氯化锑 以 乙醚 为溶剂， 以83%的产率得到[nBuC(N(iPr))2-η2]SbCl2
  参考文献：
  名称：

  重第 15 族元素的杂配脒配合物 - 合成、X 射线晶体结构和理论计算

  摘要：

  单取代的脒配合物 [RC(NR')2]ECl2 [E = Sb, R = tBu, R' = iPr 1, Cy 2, 2,6-iPr2C6H3 (Dipp) 3; R = nBu，R' = iPr 4；E = Bi, R = tBu, R' = iPr 5, Dipp 6] 通过 ECl3 与脒酸锂的盐消除反应以高产率制备。通过元素分析、核磁共振和红外光谱以及单晶 X 射线衍射对 1-6 进行了表征。此外，还进行了计算计算以阐明 1 和 5 中的不同键合模式。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  DOI：

  10.1002/ejic.200900233
• 作为产物：
  描述：

  N,N'-二异丙基碳二亚胺 、 正丁基锂 以 四氢呋喃 、 乙醚 为溶剂， 反应 18.0h， 生成 lithium N,N'-di(propan-2-yl)-n-butylamidinate
  参考文献：
  名称：

  Homoleptic Gadolinium Amidinates as Precursors for MOCVD of Oriented Gadolinium Nitride (GdN) Thin Films

  摘要：

  Five new homoleptic gadolinium tris-amidinate complexes are reported, which were synthesized via the salt-elimination reaction of GdCl3 with 3 equiv of lithiated symmetric and asymmetric amidinates at ambient temperature. The Gd-tris-amidinates [Gd{((NPr)-Pr-i)(2)CR}(3)] [R = Me (1), Et (2), Bu-t (3), Bu-n (4)] and [Gd{(NEt)((NBu)-Bu-t)CMe}(3)] (5) are solids at room temperature and sublime at temperatures of about 125 degrees C (6 x 10(-2) mbar) with the exception of compound 4, which is a viscous liquid at room temperature. According to X-ray diffraction analysis of 3 and 5 as representative examples of the series, the complexes adopt a distorted octahedral structure in the solid state. Mass spectrometric (MS) data confirmed the monomeric structure in the gas phase, and high-resolution MS allowed the identification of characteristic fragments, such as [{((NPr)-Pr-i)(2)CR}GdCH3](+) and [{((NPr)-Pr-i)(2)CR}GdNH](+). The alkyl substitution patterns of the amidinate ligands clearly show an influence on the thermal properties, and specifically, the introduction of the asymmetric carbodiimide leads to a lowering of the onset of volatilization and decomposition. Compound 5, which is the first Gd complex with an asymmetric amidinate ligand system to be reported, was, therefore, tested for the MOCVD of GdN thin films. The as-deposited GdN films were capped with Cu in a subsequent MOCVD process to prevent postdeposition oxidation of the films. Cubic GdN on Si(100) substrates with a preferred orientation in the (200) direction were grown at 750 degrees C under an ammonia atmosphere and exhibited a columnar morphology and low levels of C or O impurities according to scanning electron microscopy, Rutherford backscattering, and nuclear reaction analysis.

  DOI：

  10.1021/ic301826s

文献信息

• Scandium-Promoted Direct Conversion of Dinitrogen into Hydrazine Derivatives via N–C Bond Formation
  作者：Ze-Jie Lv、Zhe Huang、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1021/jacs.9b04293

  日期：2019.6.5

  scandium-mediated synthetic cycle affording hydrazine derivatives (RMeN-NMeR') directly from N2 and carbon-based electrophiles. The cycle includes three main steps: (i) reduction of a halogen-bridged discandium complex under N2 leading to a (N2)3--bridged discandium complex via a (N2)2- intermediate; (ii) treatment of the (N2)3- complex with methyl triflate (MeOTf), affording a (N2Me2)2--bridged discandium

  将二氮 (N2) 直接转化为有机化合物，而不是通过氨 (NH3)，从根本上和实践上都具有重要意义。在这里，我们报告了一种高效的钪介导的合成循环，可直接从 N2 和碳基亲电试剂中提供肼衍生物 (RMeN-NMeR')。该循环包括三个主要步骤： (i) 在 N2 下还原卤素桥连的二钪络合物，通过 (N2)2- 中间体生成 (N2)3--桥连的二钪络合物；(ii) 用三氟甲磺酸甲酯 (MeOTf) 处理 (N2)3- 络合物，得到 (N2Me2)2--桥接的二氧化钛络合物；(iii) (N2Me2)2-配合物与碳基亲电试剂的进一步反应，产生肼衍生物并再生卤化物前体。此外，观察到 CO 分子插入到 (N2Me2)2-钪络合物中的一个 Sc-N 键中。最值得注意的是，这是稀土金属促进 N2 直接转化为有机化合物的第一个例子；这些 (N2)3- 和 (N2Me2)2- 配合物与亲电子试剂反应形成 CN
• Group 11 Amidinates and Guanidinates: Potential Precursors for Vapour Deposition
  作者：Todd J. J. Whitehorne、Jason P. Coyle、Ahsan Mahmood、Wesley H. Monillas、Glenn P. A. Yap、Seán T. Barry

  DOI：10.1002/ejic.201100262

  日期：2011.7

  Several guanidinates of copper and silver, as well as amidinates and guanidinates of gold were synthesized as potential precursors for vapour deposition methods. These compounds were found to be dimers in the case of copper and gold, and trimers in the case of silver. The copper compounds showed good thermal and photostability, and were isolable by sublimation. The silver compounds proved to be very

  铜和银的几种胍盐以及金的脒盐和胍盐被合成为气相沉积方法的潜在前体。发现这些化合物在铜和金的情况下是二聚体，在银的情况下是三聚体。铜化合物表现出良好的热稳定性和光稳定性，并可通过升华分离。银化合物被证明对热和光都具有很强的反应性，并且发现在加热时会沉积银金属，这表明这些敏感化合物可以用作单一来源的前体。发现金化合物表现出一些热和光敏感性，但比银化合物更稳定。具体而言，发现 [Au(NiPr)2NMe2]2 (8) 在 85 °C 和 20 mTorr 下可升华，并在较高温度下沉积金金属。这些金属沉积热反应被认为是从作为还原剂的胍盐配体中提取氢。有趣的是，发现脒金化合物在加热时会产生二异丙基碳二亚胺，这表明这些化合物会去除碳二亚胺，而不是从配体中提取氢原子。
• Reactivity of lithium n-butyl amidinates towards group 14 metal(ii) chlorides providing series of hetero- and homoleptic tetrylenes
  作者：Tomáš Chlupatý、Zdeňka Padělková、Antonín Lyčka、Jiří Brus、Aleš Růžička

  DOI：10.1039/c2dt12472f

  日期：——

  group 14 metal(II) complexes were prepared by salt elimination from starting lithium amidinates and metal(II) chlorides both in stoichiometric ratio 2 : 1 and 1 : 1, respectively. The target amidinates contain less bulky isopropyl or cyclohexyl as well as a sterically demanding aromatic substituent. Desired 1 : 1 Pb(II) complexes are not accessible by the described procedure. Ligand transfer from Pb

  新的类的均聚物和杂正丁基的Ñ，Ñ '二取代amidinato第14族金属（II）配合物是由盐消除从起始锂脒盐和金属（制备II）两者氯化物的化学计量比2：1和1 ：1，分别。目标a酰胺含有较少体积的异丙基或环己基以及空间上需要的芳族取代基。所描述的程序无法获得所需的1：1 Pb（II）配合物。如果均溶性Pb（II）化合物与SnCl 2反应，则会发生从Pb到S​​n的配体转移。制备的四甲苯的特征在于1 H，13 C，在C 6 D 6或THF-d 8中的119 Sn和207 Pb NMR光谱。X射线衍射研究一种杂配Ge（ II）单体，其中三个配位锗原子的配位多面体为三角锥，杂配Sn（ II）配合物的两种不同二聚结构，一种am氢碘化物副产物以及其氧化产物四环核素杂多氯亚锡（ II）as胺盐，在中心Sn 2 O 2中具有两个Sn（ IV）和两个Sn（ II）原子在适当的单晶上进行平面环。一种杂芳亚锡
• Homoleptic Gadolinium Amidinates as Precursors for MOCVD of Oriented Gadolinium Nitride (GdN) Thin Films
  作者：Michael Krasnopolski、Cristian G. Hrib、Rüdiger W. Seidel、Manuela Winter、Hans-Werner Becker、Detlef Rogalla、Roland A. Fischer、Frank T. Edelmann、Anjana Devi

  DOI：10.1021/ic301826s

  日期：2013.1.7

  Five new homoleptic gadolinium tris-amidinate complexes are reported, which were synthesized via the salt-elimination reaction of GdCl3 with 3 equiv of lithiated symmetric and asymmetric amidinates at ambient temperature. The Gd-tris-amidinates [Gd((NPr)-Pr-i)(2)CR}(3)] [R = Me (1), Et (2), Bu-t (3), Bu-n (4)] and [Gd(NEt)((NBu)-Bu-t)CMe}(3)] (5) are solids at room temperature and sublime at temperatures of about 125 degrees C (6 x 10(-2) mbar) with the exception of compound 4, which is a viscous liquid at room temperature. According to X-ray diffraction analysis of 3 and 5 as representative examples of the series, the complexes adopt a distorted octahedral structure in the solid state. Mass spectrometric (MS) data confirmed the monomeric structure in the gas phase, and high-resolution MS allowed the identification of characteristic fragments, such as [((NPr)-Pr-i)(2)CR}GdCH3](+) and [((NPr)-Pr-i)(2)CR}GdNH](+). The alkyl substitution patterns of the amidinate ligands clearly show an influence on the thermal properties, and specifically, the introduction of the asymmetric carbodiimide leads to a lowering of the onset of volatilization and decomposition. Compound 5, which is the first Gd complex with an asymmetric amidinate ligand system to be reported, was, therefore, tested for the MOCVD of GdN thin films. The as-deposited GdN films were capped with Cu in a subsequent MOCVD process to prevent postdeposition oxidation of the films. Cubic GdN on Si(100) substrates with a preferred orientation in the (200) direction were grown at 750 degrees C under an ammonia atmosphere and exhibited a columnar morphology and low levels of C or O impurities according to scanning electron microscopy, Rutherford backscattering, and nuclear reaction analysis.
• Heteroleptic Amidinate Complexes of Heavy Group 15 Elements – Synthesis, X‐ray Crystal Structures and Theoretical Calculations
  作者：Benjamin Lyhs、Stephan Schulz、Ulrich Westphal、Dieter Bläser、Roland Boese、Michael Bolte

  DOI：10.1002/ejic.200900233

  日期：2009.5

  Monosubstituted amidinate complexes [RC(NR′)2]ECl2 [E = Sb, R = tBu, R′ = iPr 1, Cy 2, 2,6-iPr2C6H3 (Dipp) 3; R = nBu, R′ = iPr 4; E = Bi, R = tBu, R′ = iPr 5, Dipp 6] were prepared in high yields by salt elimination reactions of ECl3 with Li amidinates. 1–6 were characterized by elemental analyses, NMR and IR spectroscopy and single-crystal X-ray diffraction. In addition, computational calculations were performed

  单取代的脒配合物 [RC(NR')2]ECl2 [E = Sb, R = tBu, R' = iPr 1, Cy 2, 2,6-iPr2C6H3 (Dipp) 3; R = nBu，R' = iPr 4；E = Bi, R = tBu, R' = iPr 5, Dipp 6] 通过 ECl3 与脒酸锂的盐消除反应以高产率制备。通过元素分析、核磁共振和红外光谱以及单晶 X 射线衍射对 1-6 进行了表征。此外，还进行了计算计算以阐明 1 和 5 中的不同键合模式。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)