Cl2(13)C=P(2,4,6-tri-tert-butylphenyl) | 204275-75-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Cl2(13)C=P(2,4,6-tri-tert-butylphenyl)
• 英文别名: dichloro(113C)methylidene-(2,4,6-tritert-butylphenyl)phosphane
• CAS: 204275-75-2
• 化学式: C₁₉H₂₉Cl₂P
• 分子量: 360.308
• InChiKey: DPPBWVLXJGGWOP-LOYIAQTISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.72
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  Cl2(13)C=P(2,4,6-tri-tert-butylphenyl) 在 正丁基锂 、 叔丁基锂 作用下， 生成
  参考文献：
  名称：

  Reduction of Monophosphaallenes: An EPR Study and ab Initio Investigations of (HPCCH₂)^-• and (HPCHCH₂)^• Radicals

  摘要：

  Cyclic voltammetry shows that monophosphaallene ArP=C=C(C6H5)(2) (where Ar = (C6H2Bu3)-Bu-t-2,4,6), 1a, undergoes irreversible reduction at 2266 mV in THF. The EPR spectra of the reduction products are obtained in liquid and frozen solutions after specific C-13 enrichment of the allenic carbon atoms. The resulting hyperfine tensors are compared with those obtained from ab initio MP2, MCSCF, CI, and DFT calculations for the radical anion (HP=C=CH2)(-.) and for the monophosphaallylic radical (HP.-CH=CH2) <----> (HP=CH-(CH2)-C-.). The most elaborate treatments of the hyperfine structure (CI and DFT) indicate that the species observed by EPR is the monophosphaallylic radical.

  DOI：

  10.1021/jp982519b
• 作为产物：
  描述：

  氯仿-13C 、 2,4,6-tri-t-butylphenylphosphonous dichloride 在 正丁基锂 作用下， 生成 Cl2(13)C=P(2,4,6-tri-tert-butylphenyl)
  参考文献：
  名称：

  Characterization of transient radicals in the reduction product of the –PCCP– system: EPR and theoretical studies

  摘要：

  在室温下，通过电化学或化学还原在THF中溶解的Ar–PCCP–Ar的溶液获得的EPR光谱显示出与两个等效31P核的超精细相互作用（165 MHz）。在Ar–P13C13CP–Ar中观察到与两个等效13C的额外耦合。31P各向异性耦合常数可以从低温录得的光谱中获得。这表明未成对电子主要局域于两个磷原子上（占78%）。对两种自由基阴离子的不同异构体进行了量子化学计算（DFT和从头算SCI）：[H–PCCP–H]•–和[H–PCH–CHP–H]•–。尽管这两种物质的优化几何形状显然不同，但它们都未导致与实验结果相矛盾的13C/31P超精细张量。EPR光谱上没有任何1H分裂以及还原波的准可逆性使得识别[Ar–PCCP–Ar]•–更加可能。

  DOI：

  10.1039/b205848k

文献信息

• Nickel Complexes Containing New Carbon−Phosphorus Unsaturated Ligands:  First Examples of Phosphavinylidene−Phosphorane [R₃PCPR‘] and Phosphavinyl Phosphonium [C(H)(PR₃)P(R‘)]⁺ Ligands
  作者：Wayde V. Konze、Victor G. Young,、Robert J. Angelici

  DOI：10.1021/om970895x

  日期：1998.4.1

  Cl2CPN(SiMe3)2 with 1:2 Ni(COD)2/PPh3, Ni(PPh3)4, or (Ph3P)2Ni(C2H4) initially yields the phosphavinyl phosphonium complex Cl(Ph3P)Ni[η2-C(Cl)(PPh3)PN(SiMe3)2] (IIa). Addition of another equivalent of Ni(0) reagent to IIa results in the formation of the novel, dinuclear, phosphavinylidene−phosphorane complex Ni2Cl2(PPh3)2[μ2-η2:η2-C(PPh3)PN(SiMe3)2] (IIIa); the structure of IIIa was established by X-ray diffraction

  最初产生的Cl 2 C PN（SiMe 3）2与1：2 Ni（COD）2 / PPh 3，Ni（PPh 3）4或（Ph 3 P）2 Ni（C 2 H 4）的氧化加成反应所述phosphavinyl鏻络合物氯（PH 3 P）的Ni [η 2 -C（Cl）的（PPH 3）PN（森达3）2 ]（IIA）。向IIa中添加另一当量的Ni（0）试剂会导致形成新颖的双核磷亚磷叉膦络合物Ni2氯2（PPH 3）2 [μ 2 -η 2：η 2 -C（PPH 3）PN（森达3）2 ]（IIIa受体）; IIIa的结构是通过X射线衍射建立的，并包含一个在两个四坐标平面镍原子之间以蝶形排列的Ni 3-Ni距离过长而无法进行显着键合相互作用的Ph 3 P C PR'配体。Ph 3 P C PR'配体，可以看作是磷腈（C具有膦供体取代基的PR）配体充当两个镍原子的六电子供体。这与充当双电子供体配体的已知的R 3 P C
• EPR and theoretical studies of the reduction product of the fulvenephosphaallene system
  作者：M Chentit、H Sidorenkova、S Choua、M Geoffroy、Y Ellinger、G Bernardinelli

  DOI：10.1016/s0022-328x(01)01098-1

  日期：2001.9

  Fluoren-9-ylidenemethylene-(2,4,6-tri-tert-butyl-phenyl)phosphane (2), a new type of phosphaallene with the terminal carbone incorporated in a cyclopentadienyl ring, has been synthesized and its crystal structure has been determined. The P-31 and C-13 (central carbon) hyperfine tensors of the reduction compound of this phosphaallene have been measured on the EPR spectra recorded after electrochemical reduction of a solution of 2 in THF. Structures of the model molecules HP=C=Cp (where Cp is a cyclopentadienyl ring), [HP=C=Cp](.-) and [HP-CH=Cp](.) have been optimized by DFT and the hyperfine couplings of the paramagnetic species have been calculated by DFT and SO methods. The comparison between the experimental and the theoretical results shows that, in solution, the radical anion [2](.-) is readily protonated and that the EPR spectra are due to the phosphaallylic radical. (C) 2001 Published by Elsevier Science B.V.