(3-Tert-butylcyclopenta-2,4-dien-1-ylidene)-methyl-diphenyl-lambda5-phosphane | 1380114-64-6

• 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: (3-Tert-butylcyclopenta-2,4-dien-1-ylidene)-methyl-diphenyl-lambda5-phosphane
• 英文别名: (3-tert-butylcyclopenta-2,4-dien-1-ylidene)-methyl-diphenyl-λ5-phosphane
• CAS: 1380114-64-6
• 化学式: C₂₂H₂₅P
• 分子量: 320.414
• InChiKey: XDLTZTKXYBJGRR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.23
• 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：

  (3-Tert-butylcyclopenta-2,4-dien-1-ylidene)-methyl-diphenyl-lambda5-phosphane 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 以91%的产率得到
  参考文献：
  名称：

  New Lithium Phosphonium Diylides: A Methylene and a Cyclopentadienyl Moiety as Ylidic Coordination Sites

  摘要：

  A set of lithium phosphonium diylides Li[CH2-PR2-Cp-X] (9-12; Cp-X = C5Me4, C(5)H(3)tBu, R = Ph, Me) is presented. Two of the lithium complexes were characterized by means of single-crystal X-ray analysis, revealing a dimeric head-to-tail arrangement in the solid state. The coordination behavior of 9-12 in the liquid phase is solvent dependent These lithium phosphonium diylides exist as contact ion pairs in benzene and as solvent-separated ion pairs in THF solutions. Phosphonium salts [H3C-PR2-(CpH)-H-X)]I-+(-) (1-4) are starting materials for the syntheses of the title compounds and exist as mixtures of isomers due to [1,5]-prototropic rearrangements. The dynamic behavior in solution has been investigated. Two different routes allow access to title compounds 9-12. Reactions of 1-4 with 2 equiv of nBuLi give 9-12 in a one-pot synthesis. in an alternative two-step route, dehydrodehalogenation of 1-4 with KH gives the corresponding phosphonium ylides 5-8. Two of these phosphonium ylides were characterized by single-crystal Xray analysis. In one case two different conformers were obtained.

  DOI：

  10.1021/om201182y
• 作为产物：
  描述：

  在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以79%的产率得到(3-Tert-butylcyclopenta-2,4-dien-1-ylidene)-methyl-diphenyl-lambda5-phosphane
  参考文献：
  名称：

  New Lithium Phosphonium Diylides: A Methylene and a Cyclopentadienyl Moiety as Ylidic Coordination Sites

  摘要：

  A set of lithium phosphonium diylides Li[CH2-PR2-Cp-X] (9-12; Cp-X = C5Me4, C(5)H(3)tBu, R = Ph, Me) is presented. Two of the lithium complexes were characterized by means of single-crystal X-ray analysis, revealing a dimeric head-to-tail arrangement in the solid state. The coordination behavior of 9-12 in the liquid phase is solvent dependent These lithium phosphonium diylides exist as contact ion pairs in benzene and as solvent-separated ion pairs in THF solutions. Phosphonium salts [H3C-PR2-(CpH)-H-X)]I-+(-) (1-4) are starting materials for the syntheses of the title compounds and exist as mixtures of isomers due to [1,5]-prototropic rearrangements. The dynamic behavior in solution has been investigated. Two different routes allow access to title compounds 9-12. Reactions of 1-4 with 2 equiv of nBuLi give 9-12 in a one-pot synthesis. in an alternative two-step route, dehydrodehalogenation of 1-4 with KH gives the corresponding phosphonium ylides 5-8. Two of these phosphonium ylides were characterized by single-crystal Xray analysis. In one case two different conformers were obtained.

  DOI：

  10.1021/om201182y

文献信息

• Ruthenium cyclopentadienylidene phosphorane complexes – Synthesis, characterization and catalysis
  作者：Paul Kübler、Benjamin Oelkers、Jörg Sundermeyer

  DOI：10.1016/j.jorganchem.2014.06.002

  日期：2014.9

  The synthesis of ruthenium complexes of cyclopentadienylidene phosphorane ligands C5H3R1–PR22R3 (a: R1 = H, R2 = R3 = Ph; b: R1 = tBu, R2 = Ph, R3 = Me; c: R1 = H, R2 = R3 = nBu; d: R1 = H, R2 = Ph; R3 = NHDip with Dip = 2,6-diisopropylphenyl) is described. The influence of steric and electronic effects of these ligands on spectroscopic and structural properties is analyzed by means of NMR spectroscopy

  环戊二烯亚基膦烷配体C 5 H 3 R 1 -PR 2 2 R 3的钌配合物的合成（a：R 1  = H，R 2  = R 3  = Ph; b：R 1  =  t Bu，R 2  = Ph， R 3  ＝ Me；c：R 1  ＝ H，R 2  ＝ R 3  ＝  n Bu；d：R 1  ＝ H，R 2  ＝ Ph； R 3 描述了NHDip，其中Dip ＝ 2，6-二异丙基苯基。这些配体的空间和电子效应对光谱和结构性质的影响通过NMR光谱和X射线晶体学分析。形式的复合物的[Ru（η 5 -C 5 H ^ 3 - [R 1 -PR 2 2 - [R 3）（NCMe）3 ] [PF 6 ] 2 图3a - Ç考察了它们在代表性的烯烃-炔偶联反应中的活性。研究了在Cp部分的空间需求phospho离子标记对10-十一碳烯酸甲酯与1-辛炔偶联的收率和区域选择性的影响。
• eta5:eta1-CYCLOPENTADIENYLIDEN-PHOSPHORAN-CONSTRAINED-GEOMETRY-KOMPLEXE DER SELTENERD-METALLE
  申请人：Rockwood Lithium GmbH

  公开号：EP2739632B1

  公开（公告）日：2017-06-21
• CYCLOPENTADIENYLIDENE-PHOSPHORANE CONSTRAINED GEOMETRY COMPLEXES OF RARE EARTH METALS
  申请人：Hillesheim Nina

  公开号：US20140163187A1

  公开（公告）日：2014-06-12

  The invention relates to η 5 :η 1 -cyclopentadienylidene-phosphorane constrained geometry complexes of rare earth metals, abbreviated to η 5 :η 1 -CpPC-CGC, method for production and use of same. The η 5 :η 1 -CpPC-CGCs correspond to the general formula (1), wherein SE=Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; X=independently of one another, a mono-anionic diorganoamido-, bistrimethylsilylamido-, halogenido-, alkyl-, aryl-, alkoxo-, aryloxo- or alkylaluminate (AlR 4 − ) substituent; L=neutral ligand (PR 3 , NR 3 , pyridine), solvent molecule (THF, ether, DMF, DMSO, HMPT, tetrahydropyran THP, tetrahydrothiofuran THT); R=alkyl with up to 1-10 C atoms or mono- or polycyclical aryl with 6 to 20 C atoms; R 1 , R 4 =independently of one another H or methyl; R 2 , R 3 =independently of one another, H or methyl or tertiary butyl or together a substituted cycloalkyl group; R 5 , R 6 =methyl, n-butyl, tertiary butyl or phenyl; R 7 , R 8 =independently of one another H, trimethylsilyl, alkyl with 1-10 C atoms or mono- or polycyclical aryl with 6 to 20 C atoms, and m=0, 1, 2 or 3.
• US9200092B2
  申请人：——

  公开号：US9200092B2

  公开（公告）日：2015-12-01
• New Lithium Phosphonium Diylides: A Methylene and a Cyclopentadienyl Moiety as Ylidic Coordination Sites
  作者：Crispin Lichtenberg、Nina S. Hillesheim、Michael Elfferding、Benjamin Oelkers、Jörg Sundermeyer

  DOI：10.1021/om201182y

  日期：2012.6.11

  A set of lithium phosphonium diylides Li[CH2-PR2-Cp-X] (9-12; Cp-X = C5Me4, C(5)H(3)tBu, R = Ph, Me) is presented. Two of the lithium complexes were characterized by means of single-crystal X-ray analysis, revealing a dimeric head-to-tail arrangement in the solid state. The coordination behavior of 9-12 in the liquid phase is solvent dependent These lithium phosphonium diylides exist as contact ion pairs in benzene and as solvent-separated ion pairs in THF solutions. Phosphonium salts [H3C-PR2-(CpH)-H-X)]I-+(-) (1-4) are starting materials for the syntheses of the title compounds and exist as mixtures of isomers due to [1,5]-prototropic rearrangements. The dynamic behavior in solution has been investigated. Two different routes allow access to title compounds 9-12. Reactions of 1-4 with 2 equiv of nBuLi give 9-12 in a one-pot synthesis. in an alternative two-step route, dehydrodehalogenation of 1-4 with KH gives the corresponding phosphonium ylides 5-8. Two of these phosphonium ylides were characterized by single-crystal Xray analysis. In one case two different conformers were obtained.