dichloro(1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl)phosphine | 1198765-49-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: dichloro(1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl)phosphine
• 英文别名: Dichloro-(1,1,3,3,5,5,7,7-octaethyl-2,6-dihydro-s-indacen-4-yl)phosphane；dichloro-(1,1,3,3,5,5,7,7-octaethyl-2,6-dihydro-s-indacen-4-yl)phosphane
• CAS: 1198765-49-9
• 化学式: C₂₈H₄₅Cl₂P
• 分子量: 483.545
• InChiKey: PFEZMLKYIXVOPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.6
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  dichloro(1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl)phosphine 在 锌 作用下， 以 四氢呋喃 、 氘代甲苯 为溶剂， 反应 61.5h， 生成
  参考文献：
  名称：

  稠环大键联键保护的不对称PNP-Pincer型磷烯配体：合成及其在Rh（I）和Ir（I）配合物中的应用

  摘要：

  We recently reported that 2-(phospholanylmethyl)-6-(2-phosphaethenyl)pyridine (PPEP) with a 2,4,6-tri-tert-butylphenyl group (Mes*) as steric protection of the P=C bond serves as a noninnocent ligand on leading to extremely high reactivity toward metal ligand cooperative activation of ammonia and acetonitrile. The high reactivity is largely due to the strong pi-accepting properties of the P=C bond. However, PPEP had a stability problem that provokes the loss of the P=C bond on other transition metals, including Rh(I), and restricts its utilization. This paper describes the synthesis of Eind-PPEP protected by an octaethyl-s-hydrindacen-4-yl group (Eind) instead of Mes*. The fused ring bulky Eind group successfully prevents the loss of the P=C bond and enables us to compare the reactivity of Rh(I) and Ir(I) complexes toward ammonia. The complex K[RhCl(Eind-PPEP*)], bearing a dearomatized Eind-PPEP* ligand, undergoes simple ligand displacement to give [Rh(NH3)(Eind-PPEP*)], whereas the iridium analogue K[IrCl(Eind-PPEP*)] causes N-H bond cleavage to form [Ir(NH2)(Eind-PPEP)]. DFT calculations indicate a thermodynamic cause of the metal-dependent product change.

  DOI：

  10.1021/acs.organomet.6b00113
• 作为产物：
  描述：

  4-溴-1,1,3,3,5,5,7,7-八乙基-1,2,3,5,6,7-六氢对称引达省 在 正丁基锂 、 三氯化磷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以80%的产率得到dichloro(1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl)phosphine
  参考文献：
  名称：

  含稠环大皮组的双膦的合成与表征

  摘要：

  由稠环庞大的 1,1,3,3,5,5,7,7-octa-R-取代的 s-hydrindacen-4-yl (Rind) 基团稳定的双膦已通过以下方法获得橙色晶体相应的二氯膦 (Rind)PCl2 与萘化锂 (LiNaph)。(Eind)PCl2 和双膦的分子结构 (Eind)PP(Eind) 和 (EMind)PP(EMind) 具有庞大的 Eind 和较小的 EMind 基团，已通过 X 射线晶体学证实。PP 键的形成已通过光谱方法充分表征。

  DOI：

  10.1002/hc.21197

文献信息

• A Square-Planar Complex of Platinum(0)
  作者：Katsuhiko Takeuchi、Hiro-omi Taguchi、Ippei Tanigawa、Shota Tsujimoto、Tsukasa Matsuo、Hiromasa Tanaka、Kazunari Yoshizawa、Fumiyuki Ozawa

  DOI：10.1002/anie.201609515

  日期：2016.12.5

  The Pt0 complex [Pt(PPh3)(Eind2‐BPEP)] with a pyridine‐based PNP‐pincer‐type phosphaalkene ligand (Eind2‐BPEP) has a highly planar geometry around Pt with ∑(Pt)=358.6°. This coordination geometry is very uncommon for formal d10 complexes, and the Pd and Ni homologues with the same ligands adopt distorted tetrahedral geometries. DFT calculations reveal that both the Pt and Pd complexes are M0 species

  具有基于吡啶的PNP钳型磷烯烃配体（Eind 2 BPEP）的Pt 0络合物[Pt（PPh 3）（Eind 2 -BPEP）]在Pt周围具有高度平面的几何形状，∑（Pt）= 358.6° 。这种配位几何对于形式d 10络合物非常罕见，并且具有相同配体的Pd和Ni同源物采用扭曲的四面体几何形状。DFT计算表明Pt和Pd络合物均为M 0在金属上具有近十个价电子的物种，而它们的原子轨道占有率显然彼此不同。由于相对论效应引起的强s-d杂化，Pt络合物在原子6s轨道上占有较高的位置，因此采用了高度平面的几何形状，反映了部分未占据的轨道的形状和方向。
• π-conjugated phosphasilenes stabilized by fused-ring bulky “Rind” groups
  作者：Tsukasa Matsuo、Baolin Li、Kohei Tamao

  DOI：10.1016/j.crci.2010.07.005

  日期：2010.8

  π-conjugated phosphasilenes stabilized by bulky protecting groups based on a fused-ring octa-R-substituted s-hydrindacene skeleton (Rind groups) is reviewed. The phosphasilenes with a variety of aryl substituents at the silicon atom are covered in detail. The X-ray crystallography analysis showed the highly coplanar π-framework reinforced by the perpendicularly-fixed Rind groups. Strong π–π* absorptions have been

  摘要 综述了基于稠环八-R-取代的 s-hydrindacene 骨架（Rind 基团）的大保护基团稳定的 π-共轭磷杂环烯的化学进展。详细介绍了在硅原子上具有多种芳基取代基的磷硅烯。X 射线晶体学分析显示了由垂直固定的 Rind 基团增强的高度共面的 π 框架。已经观察到强 π-π* 吸收，证明了 π 共轭在骨架上的延伸。DFT 计算表明 LUMO 涉及 3pπ*(Si-P)–2pπ*(碳 π-电子系统)共轭的显着贡献。还包括 π 共轭磷杂环烯的金 (I) 配合物的制备。
• Unsymmetrical PNP-Pincer Type Phosphaalkene Ligands Protected by a Fused-Ring Bulky Eind Group: Synthesis and Applications to Rh(I) and Ir(I) Complexes
  作者：Hiro-omi Taguchi、Daichi Sasaki、Katsuhiko Takeuchi、Shota Tsujimoto、Tsukasa Matsuo、Hiromasa Tanaka、Kazunari Yoshizawa、Fumiyuki Ozawa

  DOI：10.1021/acs.organomet.6b00113

  日期：2016.5.23

  We recently reported that 2-(phospholanylmethyl)-6-(2-phosphaethenyl)pyridine (PPEP) with a 2,4,6-tri-tert-butylphenyl group (Mes*) as steric protection of the P=C bond serves as a noninnocent ligand on leading to extremely high reactivity toward metal ligand cooperative activation of ammonia and acetonitrile. The high reactivity is largely due to the strong pi-accepting properties of the P=C bond. However, PPEP had a stability problem that provokes the loss of the P=C bond on other transition metals, including Rh(I), and restricts its utilization. This paper describes the synthesis of Eind-PPEP protected by an octaethyl-s-hydrindacen-4-yl group (Eind) instead of Mes*. The fused ring bulky Eind group successfully prevents the loss of the P=C bond and enables us to compare the reactivity of Rh(I) and Ir(I) complexes toward ammonia. The complex K[RhCl(Eind-PPEP*)], bearing a dearomatized Eind-PPEP* ligand, undergoes simple ligand displacement to give [Rh(NH3)(Eind-PPEP*)], whereas the iridium analogue K[IrCl(Eind-PPEP*)] causes N-H bond cleavage to form [Ir(NH2)(Eind-PPEP)]. DFT calculations indicate a thermodynamic cause of the metal-dependent product change.
• Synthesis and Characterization of Diphosphenes Bearing Fused-Ring Bulky Rind Groups
  作者：Baolin Li、Shota Tsujimoto、Yongming Li、Hayato Tsuji、Kohei Tamao、Daisuke Hashizume、Tsukasa Matsuo

  DOI：10.1002/hc.21197

  日期：2014.11

  the fused-ring bulky 1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacen-4-yl (Rind) groups have been obtained as orange crystals by the reduction of the corresponding dichlorophosphines, (Rind)PCl2, with lithium naphthalenide (LiNaph). The molecular structures of (Eind)PCl2 and the diphosphenes, (Eind)PP(Eind) and (EMind)PP(EMind), having the bulky Eind and the less bulky EMind groups, have been confirmed

  由稠环庞大的 1,1,3,3,5,5,7,7-octa-R-取代的 s-hydrindacen-4-yl (Rind) 基团稳定的双膦已通过以下方法获得橙色晶体相应的二氯膦 (Rind)PCl2 与萘化锂 (LiNaph)。(Eind)PCl2 和双膦的分子结构 (Eind)PP(Eind) 和 (EMind)PP(EMind) 具有庞大的 Eind 和较小的 EMind 基团，已通过 X 射线晶体学证实。PP 键的形成已通过光谱方法充分表征。