1-piperidinyloxy-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl radical

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 1-piperidinyloxy-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl radical
• 化学式: C₂₁H₂₈N₂O₂P
• 分子量: 371.439
• InChiKey: JNNYHANJPYMLNP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  33.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-piperidinyloxy-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl radical 在 苯肼 作用下， 以 氘代氯仿 为溶剂， 生成 N-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)-P,P-diphenyl-phosphinic amide
  参考文献：
  名称：

  合成，晶体结构，并与次膦酰胺TEMPO自由基和构造的4种配位化合物磁行为[M（HFAC）2 ]（M =铜II，钴II，锰II）†

  摘要：

  在本工作中，我们描述了通过组装含有TEMPO部分的新次膦酰胺，1-哌啶基氧基-4-[（二苯基膦基）氨基] -2、2、6、6获得的四种配位化合物的合成，晶体结构和磁性。 -四甲基自由基（dppnTEMPO），具有[M（hfac）2 ]构件（M = Cu II，Co II和Mn II）。配位化合物的晶体结构揭示了官能化自由基提供离散或扩展结构的有用性。在铜化合物（1）中，配体通过NP O键的氧原子配位至金属，该金属以正方形金字塔或八面体几何形状存在。对于钴和锰配合物（2-4），次膦酰胺和一氧化氮氧原子都参与了与金属的配位，从而形成一维系统。在钴络合物（2）中，由于次膦酰胺基团的氧原子被2个钴（II）离子配位，因此在之字形链中获得了有趣的自旋拓扑。配位化合物的磁行为显示出涉及金属离子和有机基团的总体反铁磁相互作用。进行DFT计算是为了分配磁性相互作用的主要路径。

  DOI：

  10.1039/c4dt01444h
• 作为产物：
  描述：

  1-piperidinyloxy-4-[(diphenylphosphanyl)amino]-2,2,6,6-tetramethyl 在 双氧水 作用下， 以80%的产率得到1-piperidinyloxy-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl radical
  参考文献：
  名称：

  Novel P,P-diphenylphosphinic amide-TEMPO radicals family: Synthesis, crystal structures, spectroscopic characterization, magnetic properties and DFT calculations

  摘要：

  A new family of three P,P-diphenylphosphinic amide-TEMPO radicals with general formula (C6H5)(2)P(X)-NH-TEMPO, X = O (1), S (2) and Se (3) were obtained by reaction of chlorodiphenylphosphine with 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl radical (NH2-TEMPO) and subsequent oxidation with H2O2 and elemental sulfur or selenium. These radicals were characterized by UV-Vis, FT-IR and H-1, P-31 and Se-77 nuclear magnetic resonance spectroscopy. The crystal structures of all radicals were determined by single-crystal X-ray diffraction. The magnetic study of all diphenylphosphinic amide-TEMPO radicals reveals very weak intermolecular ferromagnetic interactions. Density functional theory (DFT) calculations have been also performed to support the interpretation of magnetic properties and electronic structure. (C) 2018 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2018.01.011

文献信息

• A new family of multinuclear mixed-ligand copper(II) clusters: Crystal structures, magnetic properties and catecholase-like activity
  作者：Sergiu Calancea、Samira G. Reis、Guilherme P. Guedes、Rafael A. Allão Cassaro、Felipe Semaan、Fernando López-Ortiz、Maria G.F. Vaz

  DOI：10.1016/j.ica.2016.07.057

  日期：2016.11

  nuclearities: [Cu3(μ-OH)(μ-dppi)3(μ-hfac)3] (1), [Cu4(μ-dppi)4(Hdppi)2(hfac)4] (2), [Cu5(μ-O)2(μ-dppi)(μ-Hdppi)2(μ-hfac)3(hfac)2] (3) and [Cu6(μ-O)2(μ-dppi)2(μ-Hdppi)(μ-hfac)6] (4), where hfac = hexafluoroacetylacetonate, dppi = diphenylphosphinate and Hdppi = diphenylphosphinic acid. Complexes 3 and 4 are the first examples of copper(II) clusters containing a μ-oxo oxygen atom and hfac as bridging ligands.

  摘要在这项工作中，我们报告了一个获得不同核数的混合配体铜（II）簇族：[Cu3（μ-OH）（μ-dppi）3（μ-hfac）3]（1），[Cu4（μ -dppi）4（Hdppi）2（hfac）4]（2），[Cu5（μ-O）2（μ-dppi）（μ-Hdppi）2（μ-hfac）3（hfac）2]（3）和[Cu6（μ-O）2（μ-dppi）2（μ-Hdppi）（μ-hfac）6]（4），其中hfac =六氟乙酰丙酮酸酯，dppi =二苯基次膦酸酯，Hdppi =二苯基次膦酸。配合物3和4是包含μ-氧代氧原子和hfac作为桥连配体的铜（II）簇的第一个实例。所有化合物的磁性能均显示出主要的反铁磁相互作用，并使用基于自旋拓扑结构的各向同性交换模型评估了磁耦合常数。对于等边环状三核配合物（1）观察到自旋失意现象，因此，反对称交换项也被认为适合实验磁数据。获得的J值在-89cm-1至1.7cm-1的范
• Binuclear Lanthanide-Radical Complexes Featuring Two Centers with Different Magnetic and Luminescence Properties
  作者：Samira G. Reis、Matteo Briganti、Stéphane Soriano、Guilherme P. Guedes、Sergiu Calancea、Carmen Tiseanu、Miguel A. Novak、Miguel A. del Águila-Sánchez、Federico Totti、Fernando Lopez-Ortiz、Marius Andruh、Maria G. F. Vaz

  DOI：10.1021/acs.inorgchem.6b01616

  日期：2016.11.21

  Binuclear complexes with general formula [Ln(2)(hfac)(6)(H2O)(2)(dppnTEMPO)] (Ln(III) = Gd, Tb, and Dy) have been obtained using the paramagnetic ligand 1-piperidinyl-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl (dppnTEMPO) as a bridge. One of the lanthanide ions is ferromagnetically coupled with the TEMPO moiety. Two of the complexes (Dy and Tb) show slow relaxation of the magnetization, and the non-magneto-equivalence of the two Ln(III) ions was clearly observed. The ab initio CASSCF calculations were employed to confirm this behavior, as well as to rationalize the LnRad interaction. The simulations of the magnetic properties were allowed by the insights given by the calculations. The inequivalence of the Tb-III ions was also proved by emission spectroscopy.
• Synthesis, crystal structures and magnetic behaviour of four coordination compounds constructed with a phosphinic amide-TEMPO radical and [M(hfac)₂] (M = Cu^II, Co^IIand Mn^II)
  作者：Samira G. Reis、Miguel A. del Águila-Sánchez、Guilherme P. Guedes、Glaucio B. Ferreira、Miguel A. Novak、Nivaldo L. Speziali、Fernando López-Ortiz、Maria G. F. Vaz

  DOI：10.1039/c4dt01444h

  日期：——

  In the present work we describe the synthesis, crystal structures and magnetic properties of four coordination compounds obtained by assembling a new phosphinic amide containing the TEMPO moiety, 1-piperidinyloxy-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl radical (dppnTEMPO), with [M(hfac)2] building blocks (M = CuII, CoII, MnII). The crystal structures of the coordination compounds revealed

  在本工作中，我们描述了通过组装含有TEMPO部分的新次膦酰胺，1-哌啶基氧基-4-[（二苯基膦基）氨基] -2、2、6、6获得的四种配位化合物的合成，晶体结构和磁性。 -四甲基自由基（dppnTEMPO），具有[M（hfac）2 ]构件（M = Cu II，Co II和Mn II）。配位化合物的晶体结构揭示了官能化自由基提供离散或扩展结构的有用性。在铜化合物（1）中，配体通过NP O键的氧原子配位至金属，该金属以正方形金字塔或八面体几何形状存在。对于钴和锰配合物（2-4），次膦酰胺和一氧化氮氧原子都参与了与金属的配位，从而形成一维系统。在钴络合物（2）中，由于次膦酰胺基团的氧原子被2个钴（II）离子配位，因此在之字形链中获得了有趣的自旋拓扑。配位化合物的磁行为显示出涉及金属离子和有机基团的总体反铁磁相互作用。进行DFT计算是为了分配磁性相互作用的主要路径。
• Novel P,P-diphenylphosphinic amide-TEMPO radicals family: Synthesis, crystal structures, spectroscopic characterization, magnetic properties and DFT calculations
  作者：Samira G. Reis、Miguel A. del Águila-Sánchez、Guilherme P. Guedes、Yolanda Navarro、Rafael A. Allão Cassaro、Glaucio B. Ferreiraa、Sergiu Calancea、Fernando López-Ortiz、Maria G. F. Vaz

  DOI：10.1016/j.poly.2018.01.011

  日期：2018.4

  A new family of three P,P-diphenylphosphinic amide-TEMPO radicals with general formula (C6H5)(2)P(X)-NH-TEMPO, X = O (1), S (2) and Se (3) were obtained by reaction of chlorodiphenylphosphine with 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl radical (NH2-TEMPO) and subsequent oxidation with H2O2 and elemental sulfur or selenium. These radicals were characterized by UV-Vis, FT-IR and H-1, P-31 and Se-77 nuclear magnetic resonance spectroscopy. The crystal structures of all radicals were determined by single-crystal X-ray diffraction. The magnetic study of all diphenylphosphinic amide-TEMPO radicals reveals very weak intermolecular ferromagnetic interactions. Density functional theory (DFT) calculations have been also performed to support the interpretation of magnetic properties and electronic structure. (C) 2018 Elsevier Ltd. All rights reserved.