| 1597709-63-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环化合物
• CAS: 1597709-63-1
• 化学式: C₁₂H₂₇BN₂O
• 分子量: 226.17
• InChiKey: AJDSMDGWKYGKAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.22
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  15.71
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  diazaborolidine 、 potassium tert-butylate 以 四氢呋喃 、 正戊烷 为溶剂， 反应 1.0h， 以39%的产率得到
  参考文献：
  名称：

  K–H₃C and K–Sn Interactions in Potassium Trimethylstannyl Complexes: A Structural, Mechanochemical, and NMR Study

  摘要：

  A series of trimethylstannyl potassium complexes [K(L)SnMe3] with different auxiliary ligands L (L = 18-C-6, (TMEDA)(2) (TMEDA = tetramethylethylenediamine), and (12-C-4)(2)) were synthesized by alkoxide-induced B-Sn bond cleavage. X-ray structure determinations were performed for all these complexes, and the structural chemistry was studied in detail. For L = 18-C-6 and (TMEDA)(2) the solid state structures comprise polymeric [K(L)SnMe3](n) chains containing bidentate trimethylstannyl anions bridging two [K(L)](+) ions, featuring unsymmetrical coordination of the [K(L)](+) ion by K-Sn and K-H3C interactions as a central structural motif. In contrast, for L = (12-C-4)(2), separated [K(12-C-4)(2)](+) and [SnMe3](-) ions are observed. Unexpectedly, in the presence of tetrahydrofuran (THF), [K(18-C-6)SnMe3](n) forms upon crystallization a new species consisting of separated [K(18-C-6)(THF)(2)](+) and [(Me2SnCH3)K(18-C-6)SnMe(3)r](-) ions. In this unsymmetrical anion two trimethylstannyl anions coordinate a single [K(18-C-6)](+) ion; one trimethylstannyl anion coordinates via a K-Sn interaction, and the second coordinates via a K-H3C interaction. Simulations of the mechanochemical properties (compliance constants) applying approximated density functional theory revealed that both interactions are very soft and are of comparable strength. Moreover, according to our gas phase simulations the unsymmetrically coordinated [(Me2SnCH3)K(18-C-6)SnMe3](-) is indeed thermodynamically favored over both possible symmetrical isomers with either K-Sn or KH3C coordination. Furthermore, the existence of multiple species due to the two coordination modes and aggregates of [K(18-C-6)SnMe3] in solution is suggested by NMR spectroscopic studies using H-1, NOESY/ROESY, and H-1 pulsed field gradient diffusion experiments.

  DOI：

  10.1021/ic500065s

文献信息

• Elusive Phosphine Copper(I) Boryl Complexes: Synthesis, Structures, and Reactivity
  作者：Corinna Borner、Lisa Anders、Kai Brandhorst、Christian Kleeberg

  DOI：10.1021/acs.organomet.7b00775

  日期：2017.12.26

  We report the first isolation of phosphine copper boryl complexes—species pivotal to numerous copper-catalyzed borylation reactions. The reaction of diboron(4) derivatives with copper tert-butoxide complexes of phosphine ligands allows the isolation of the dimeric μ-boryl-bridged Cu(I) complexes [(iPr3P)Cu–Bdmab]2 (4) and [(C6H4(Ph2P)2)Cu–Bpin]2 (6) with Cu···Cu distances of 2.24–2.27 Å (dmab = (NMe)2C6H4

  我们报道了首次分离出磷化氢铜硼酸酯配合物-对许多铜催化的硼酸酯化反应至关重要的物种。Diboron（4）衍生物与膦配体的叔丁醇铜配合物的反应可分离出二聚体μ-硼基桥接的Cu（I）配合物[（i Pr 3 P）Cu–Bdmab] 2（4）和[ （C 6 H 4（Ph 2 P）2）Cu–Bpin] 2（6），Cu···Cu距离为2.24–2.27Å（dmab =（NMe）2 C 6 H 4，pin =（OCMe 2）2个））。在空间上要求更高的硼基配体提供了空前的多核铜硼基络合物[（i Pr 3 P）2 Cu 8（B（i PrEn））3（O t Bu）3 ]（5），是一种潜在的中间体分解。初始的Cu（I）硼基络合物（i PrEn =（N i Pr）2 C 2 H 4）。所有配合物均通过单晶X射线衍射，NMR光谱和元素分析进行​​表征。DFT计算支持这些独特复合物的性质，并深入了解其电子结构。