LiCD2CH2CH2CH3 | 203396-92-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 饱和烃
• 英文名称: LiCD2CH2CH2CH3
• CAS: 203396-92-3
• 化学式: C₄H₉Li
• 分子量: 66.0406
• InChiKey: MZRVEZGGRBJDDB-CUOKRTIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.37
• 重原子数：
  5.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  [(Me3SiNCH2CH2)3N]WCl 、 LiCD2CH2CH2CH3 生成 [(Me3SiNCH2CH2)3N]W(*C-Pr(n))
  参考文献：
  名称：

  合成和钨（IV）的烷基配合物的分解包含一个[（ME 3 SiNCH 2 CH 2）3 N] 3 -配位体

  摘要：

  多种钨烷基类型的络合物的合成[N 3 N] WR（[N 3 N] 3 - = [（ME 3 SiNCH 2 CH 2）3 N] 3 - ; R =甲基，乙基，卜，通过[N 3 N] WCl络合物的烷基化尝试CH 2 Ph，CH 2 SiMe 3，CH 2 CMe 3，环丙基，环丁基，环戊基，环己基，环戊烯基）。只能分离出甲基，苯基和环戊烯基配合物。[N 3 N] WR配合物的磁化率与[N 3N] WCl; 由于自旋轨道效应和低对称配体场分量的组合，有效力矩被抑制，导致d 2基态自旋三重态的零场分裂。由于α，α-脱氢而产生分子氢和亚烷基配合物[N 3 N] W⋮CR' ，因此未观察到线性烷基配合物。[N 3 N] W（环丙基）在一级过程中析出乙烯，生成[N 3 N] W⋮CH，而[N 3 N] W（环丁基）转化为1-钨环戊烯络合物[N 3 X射线研究证实为N] W（CHCH 2 CH 2 CH

  DOI：

  10.1021/om970670m

文献信息

• Formation of Olefins Upon Oxidation of Molybdenum Alkyl Carbynes. Organic Radical Reactivity in an Organometallic Radical Cation
  作者：Thomas K. Schoch、Stephen D. Orth、Michael C. Zerner、Karl Anker Jorgensen、Lisa McElwee-White

  DOI：10.1021/ja00129a009

  日期：1995.6

  Decomposition of the complexes (eta(5)-C5H5)(CO)P(OMe)(3)}Mo=CR [R = c-C4H9, (CH2)(3)CH3, and CH(CH2-CH2CH3)(2)] in CHCl3 results in conversion of the carbyne ligand to a terminal olefin. The reaction is initiated by oxidation and occurs during photolysis in CHCl3 or upon slow diffusion of O-2 into the reaction mixtures. Corroborating evidence for initiation of the reaction by electron transfer has been obtained by conversion of the butyl carbyne ligand of (eta(5)-C5H5)(CO)P(OMe)(3)}Mo=C(CH2)(3)CH3 to 1-pentene upon electrochemical oxidation. Mechanistic studies were consistent with H-abstraction by the carbyne radical cation to yield a cationic carbene complex which forms the olefin in a H-shift process. INDO calculations on the carbyne radical cation [(eta(5)-C5H5)(CO)P(OMe)(3)}Mo=CCH2CH3](.+) indicate stabilization upon bending the Mo=C-C angle from 180 degrees to 120 degrees. This change in geometry places spin density on the carbyne carbon in the radical cation although the initial oxidation occurs from an orbital that is primarily nonbonding metal d in character. The oxidized carbyne is thus able to function as a carbon-centered radical and abstract a hydrogen atom at the carbyne carbon. Although the olefin-forming reaction is general far alkyl carbynes with a hydrogen on C2, the tert-butyl carbyne (eta(5)-C5H5)(CO)P(OMe)(3)}Mo=CC(CH3)(3) (2e) did not form an olefin upon oxidation. Instead, photolysis of 2e in CHCl3 yielded the dichloromolybdenum carbyne (eta(5)-C5H5)Cl-2P(OMe)(3)}Mo=CC(CH3)(3) (5e) via a Cl-abstraction pathway.