K[1,1',3-(Si(CH3)3)3C3H2] | 629663-15-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: K[1,1',3-(Si(CH3)3)3C3H2]
• CAS: 629663-15-6
• 化学式: C₁₂H₂₉KSi₃
• 分子量: 296.717
• InChiKey: YHLQCYPFQGIQOZ-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  chromium dichloride 、 K[1,1',3-(Si(CH3)3)3C3H2] 以 四氢呋喃 为溶剂， 以47%的产率得到bis(1,1',3-tris(trimethylsilyl)allyl)chromium(II)
  参考文献：
  名称：

  铬与三甲基甲硅烷基化配体的均质烯丙基配合物。{[1-（SiMe 3）C 3 H 4 ] 2 Cr} 2，[1,3-（SiMe 3）2 C 3 H 3 ] 2 Cr和[1,1'，3- （SiMe 3）3 C 3 H 2 ] 2 Cr

  摘要：

  两当量的K [1-（SiMe 3）C 3 H 4 ]，K [1,3-（SiMe 3）2 C 3 H 3 ]或K [1,1'，3-（SiMe 3）反应3 C 3 H 2 ]和CrCl 2在-78°C下的THF中生成红色络合物{[1-（SiMe 3）C 3 H 4 ] 2 Cr} 2（1），[1,3-（SiMe 3）2 C 3 H 3 ] 2 Cr（2）和[1,1'，3-（SiMe3）3 C 3 H 2 ] 2 Cr（3）。它们是热稳定的化合物，对于单体2和3来说非常明显，它们具有正式的12电子计数。单晶X射线结构证实了{[1-（SiMe 3）C 3 H 4 ] 2 Cr} 2的二聚性质，它是围绕CrCr'= 1.9784（7）的Cr 2核构造的。在单体络合物中，烯丙基配体以三全能方式与金属键合，CrC距离为2.193（2）–2.257（2）Åin 2和2.223（5）–2.319（5）Åin

  DOI：

  10.1016/s0022-328x(03)00603-x

文献信息

• σ- vs π-Bonding in Manganese(II) Allyl Complexes
  作者：Laura K. Engerer、Christin N. Carlson、Timothy P. Hanusa、William W. Brennessel、Victor G. Young

  DOI：10.1021/om300478v

  日期：2012.9.10

  Reaction of two equivalents of K[1,3-(SiMe3)(2)C3H3] (= K[A']) with MnCl2 in THF produces the allyl complex A'Mn-2(thf)(2); if the reaction is conducted in ether, the solvent-free heterometallic manganate species K(2)MnA'(4) is isolated instead. With the related ally] K[1,1',3-(SiMe3)(3)C3H2] (= K[A '']), reaction with MnCl2 in THF/TMEDA produces the corresponding adduct A '' Mn-2(tmeda). In the solid state, both A'Mn-2(thf)(2) and A '' Mn-2(tmeda) are monomeric complexes with a-bonded ally! ligands (Mn-C = 2.174(2) and 2.189(2) angstrom, respectively). In contrast, K(2)MnA'(4) is a two-dimensional coordination polymer, in which two of the allyl ligands on the Mn cation are sigma-bonded (Mn-C = 2.197(6), 2.232(7) A) and the third is pi-bonded (Mn-C = 2.342(7)-2.477(7) angstrom). Both sigma-allyls are pi-coordinated to potassium cations, promoting the polymer in two directions; the pi-allyl ligand is terminal. Density functional theory (DFT) calculations indicate that isolated high-spin (C3R2H3)(2)Mn (R = H, SiMe3) complexes would possess pi-bound ligands. A mixed hapticity (pi-allyl) (sigma-allyl)MnE structure would result with the addition of either a neutral ligand (e.g., THF, MeCN) or one that is charged (Cl, H). Both allyl ligands in a bis(allyl)manganese complex are expected to adopt a sigma-bonded mode if two THF ligands are added, as is experimentally observed in A'Mn-2(thf)(2). The geometry of allyl-Mn(II) bonding is readily modified; DFT results predict that [(C3H5)Mn](+) and (C3H5)MnCl should be sigma-bonded, but the allyl in (C3H5)MnH is found to exhibit a symmetrical if-bonded arrangement. Some of this behavior is reminiscent of that found in bis(allyl)magnesium chemistry.