[(η5-C5Me5)Cr(CH2SiMe3)2] | 147423-65-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [(η5-C5Me5)Cr(CH2SiMe3)2]
• 英文别名: bis(trimethylsilylmethyl)(η(5)-pentamethylcylopentadienyl)chromium(III)；Chromium(3+);methanidyl(trimethyl)silane;1,2,3,4,5-pentamethylcyclopenta-1,3-diene
• CAS: 147423-65-2
• 化学式: C₁₈H₃₇CrSi₂
• 分子量: 361.659
• InChiKey: VEDOYIFGFCOHFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.34
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [(η5-C5Me5)Cr(CH2SiMe3)2] 以 正戊烷 为溶剂， 以67%的产率得到(Me5C5)2Cr2(μ-CH2Si(CH3)2CH2-μ-CHSi(CH3)3)
  参考文献：
  名称：

  Structure and Reactivity of Trimethylsilylmethyl Complexes of Chromium, Including the 13-Electron Alkyl Cp*Cr(CH₂SiMe₃)₂

  摘要：

  Alkylation of Cp*Cr(THF)Cl-2 with 1 or 2 equiv of LiCH2SiMe3 yielded the paramagnetic chromium alkyls [Cp*Cr(mu-Cl)(CH2SiMe3)](2) (1), Cp*Cr(CH2SiMe3)(2) (2), and Cp*Cr(L)(CH2SiMe3)(2) (3a, L = py; 3b, L = THF). Compound 2 isa coordinatively unsaturated, pseudo-five-coordinate Cr-III complex with a 13-electron configuration, and it catalyzes the polymerization of ethylene. The thermal decomposition of 2 in noncoordinating solvents proceeded via an intermediate, namely the bis(mu-alkylidene) complex [Cp*Cr(mu-CHSi(CH3)(3))](2) (4). Compound 4 suffered reductive elimination to yield the dinuclear Cr-II alkyl Cp*Cr-2(2)(mu-CH2Si(CH3)(2)CH2-mu-CHSi(CH3)(3)) (5). In contrast, the decomposition of 2 in THF, i.e., 3b, yielded the metallacycles Cp*Cr(L)(CH2)(2)Si(CH3)(3)) (6a, L = py; 6b, L = THF). Compounds 1, 2, 3b, 4, and 5 have been structurally characterized by X-ray diffraction. The reactions of 2 are rationalized in terms of competing alpha- and gamma-hydrogen elimination processes yielding terminal alkylidene and metallacyclobutane intermediates existing in equilibrium.

  DOI：

  10.1021/om980796z
• 作为产物：
  描述：

  trichlorotris(tetrahydrofuran)chromium(III) 、 pentamethylcyclopentadienyllithium 、 trimethylsilylmethyllithium 以 四氢呋喃 为溶剂， 以60%的产率得到[(η5-C5Me5)Cr(CH2SiMe3)2]
  参考文献：
  名称：

  Structure and Reactivity of Trimethylsilylmethyl Complexes of Chromium, Including the 13-Electron Alkyl Cp*Cr(CH₂SiMe₃)₂

  摘要：

  Alkylation of Cp*Cr(THF)Cl-2 with 1 or 2 equiv of LiCH2SiMe3 yielded the paramagnetic chromium alkyls [Cp*Cr(mu-Cl)(CH2SiMe3)](2) (1), Cp*Cr(CH2SiMe3)(2) (2), and Cp*Cr(L)(CH2SiMe3)(2) (3a, L = py; 3b, L = THF). Compound 2 isa coordinatively unsaturated, pseudo-five-coordinate Cr-III complex with a 13-electron configuration, and it catalyzes the polymerization of ethylene. The thermal decomposition of 2 in noncoordinating solvents proceeded via an intermediate, namely the bis(mu-alkylidene) complex [Cp*Cr(mu-CHSi(CH3)(3))](2) (4). Compound 4 suffered reductive elimination to yield the dinuclear Cr-II alkyl Cp*Cr-2(2)(mu-CH2Si(CH3)(2)CH2-mu-CHSi(CH3)(3)) (5). In contrast, the decomposition of 2 in THF, i.e., 3b, yielded the metallacycles Cp*Cr(L)(CH2)(2)Si(CH3)(3)) (6a, L = py; 6b, L = THF). Compounds 1, 2, 3b, 4, and 5 have been structurally characterized by X-ray diffraction. The reactions of 2 are rationalized in terms of competing alpha- and gamma-hydrogen elimination processes yielding terminal alkylidene and metallacyclobutane intermediates existing in equilibrium.

  DOI：

  10.1021/om980796z

文献信息

• Unusual Transformations of a Bipyridine Ligand in Attempts to Trap a Terminal Chromium(III) Alkylidene
  作者：Somying Leelasubcharoen、Kin-Chung Lam、Thomas E. Concolino、Arnold L. Rheingold、Klaus H. Theopold

  DOI：10.1021/om0007421

  日期：2001.1.1

  (η5-pentamethylcyclopentadienyl)(2-(2‘ ‘,2‘ ‘-dimethyl-2‘ ‘-silapropyl)-1,2-dihydro[2,2‘]bipyridine-1,3‘ ‘-diyl)chromium(III) (3) was obtained by a reaction of Cp*(THF)Cr(CH2)2SiMe2 with 1 equiv of 2,2‘-bipyridine (bipy). 3 is formed by carbon−carbon bond formation between one terminus of the metallacyle and the 2-position of the bipy ligand, at the expense of the aromaticity of a pyridyl group. Single-electron

  尝试陷阱终端铬亚烷基二烷基通过CP的反应*的Cr（CH 2森达3）2（CP * =η 5 -C 5我5）或金属环的CP *（THF）的Cr（CH 2）2森达2与二齿配体1,2-双（dimethyphosphino）乙烷（DMPE）导致的双核铬顺烷基的[CP *的Cr（CH 2森达3）2 ] 2（μ-η 1：η 1 -DMPe）（1）和混合[CP * Cr（CH 2）2 Si（CH 3）2 ]2（μ-η 1：η 1 -DMPe）（2），分别。在另一方面，异常单核铬配合物（η 5 -五甲基）（2-（2' ”，2' ' -二甲基-2' '-silapropyl）-1,2-二氢[2,2']联吡啶通过CP *（THF）Cr（CH 2）2 SiMe 2与1当量的2,2'-联吡啶（bipy）反应获得1,3''-二基）铬（III）（3）。3是通过在金属壳的一个末端和联吡啶配体的2-位之间形成碳-碳键而形成
• α-Olefin Polymerization with Ether-Coordinated Chromium(III) Alkyls
  作者：Paul A. White、Joe Calabrese、Klaus H. Theopold

  DOI：10.1021/om960697q

  日期：1996.12.24

  Extremely substitution labile chromium(III) alkyls of the type [Cp*Cr(OR2)nCH2SiMe3]+[B(3,5-(CF3)2C6H3)4]- (R = Me, Et, iPr; n = 1, 2) have been prepared; they are homogeneous catalysts for the polymerization of ethylene and, for the first time, α-olefins (propene, 1-hexene).

  类型为[Cp * Cr（OR 2）n CH 2 SiMe 3 ] + [B（3,5-（CF 3）2 C 6 H 3）4 ]的极度取代的不稳定铬（III）烷基-（R = Me ，Et，i Pr; n = 1，2）已经准备好; 它们是乙烯和α-烯烃（丙烯，1-己烯）的聚合反应的均相催化剂。