Me3PC5Me4 | 1380114-65-7

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: Me3PC5Me4
• 英文别名: (3-Tert-butylcyclopenta-2,4-dien-1-ylidene)-trimethyl-lambda5-phosphane；(3-tert-butylcyclopenta-2,4-dien-1-ylidene)-trimethyl-λ5-phosphane
• CAS: 1380114-65-7
• 化学式: C₁₂H₂₁P
• 分子量: 196.273
• InChiKey: BBWQSAFPSQCMEX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 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：

  Me3PC5Me4 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 以67%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82%的产率得到Me3PC5Me4
  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

• η5:η1-cyclopentadienylidene-phosphorane constrained geometry complexes of rare earth metals
  申请人：Hillesheim Nina

  公开号：US09200092B2

  公开（公告）日：2015-12-01

  The invention relates to η5:η1-cyclopentadienylidene-phosphorane constrained geometry complexes of rare earth metals, abbreviated to η5:η1-CpPC-CGC, method for production and use of same. The η5:η1-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 (AlR4−) substituent; L=neutral ligand (PR3, NR3, 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; R1, R4=independently of one another H or methyl; R2, R3=independently of one another, H or methyl or tertiary butyl or together a substituted cycloalkyl group; R5, R6=methyl, n-butyl, tertiary butyl or phenyl; R7, R8=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.

  本发明涉及稀土金属η5:η1-环戊二烯基膦烷约束几何配合物，简称为η5:η1-CpPC-CGC，以及其制备和使用方法。η5:η1-CpPC-CGCs对应于一般式（1），其中SE = Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu；X = 单烷基二元氨基、双三甲基硅氨基、卤素、烷基、芳基、烷氧基、芳氧基或烷基铝酸盐（AlR4−）取代基；L = 中性配体（PR3、NR3、吡啶）、溶剂分子（THF、醚、DMF、DMSO、HMPT、四氢吡喃THP、四氢噻吩THT）；R = 具有1-10个碳原子的烷基或具有6-20个碳原子的单环或多环芳基；R1、R4 = 独立的氢或甲基；R2、R3 = 独立的氢或甲基或叔丁基或一起被取代的环烷基；R5、R6 = 甲基、正丁基、叔丁基或苯基；R7、R8 = 独立的氢、三甲基硅基、具有1-10个碳原子的烷基或具有6-20个碳原子的单环或多环芳基，m = 0、1、2或3。
• 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