CpFe(dmpe){B(NMe2)Cl} | 1221415-27-5

• 英文名称: CpFe(dmpe){B(NMe2)Cl}
• 英文别名: CpFe(κ2-1,2-bis(dimethylphosphino)ethane)(B(NMe2)Cl)
• CAS: 1221415-27-5
• 化学式: C₁₃H₂₇BClFeNP₂
• 分子量: 361.423
• InChiKey: HEUXWBXICIAZCW-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  CpFe(dmpe){B(NMe2)Cl} 在 trimethoxonium tetrafluoroborate 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以20%的产率得到CpFe(dmpe)B(NMe2)F
  参考文献：
  名称：

  取代基对硼砂和硼化铁体系的影响：异常的反应性和光谱性质

  摘要：

  合成研究表明，金属结合的辅助配体L和硼结合的取代基X的位阻和电子性质在甲硼烷基（L n MBX 2）和甲硼烷基体系的结构和反应化学中起着至关重要的作用。 （L n MBX）。因此，三烷基膦配体的强σ供体特性反映在以下事实中：[CpFe（dmpe）（BOMes）] +被证明是一种易于处理的，在室温下稳定的物质，而[CpFe（CO）2（BOMes） ] +不是。此外，增强的空间轮廓dmpe（与二羰基辅助配体组相比）的变化显示出会影响硼烷基氨基取代基上亲电烷基化的倾向，例如在CpFe（dmpe）{B（NMe 2）Cl} vs. CpFe（CO）2 {B（ NMe 2）Cl}。X取代基本身内的立体因素也至关重要，例如，可以为存在[Me 3 O] [BF 4 ]时NMe 2和NCy 2取代基具有不同的不稳定性提供理论依据。此外，B–X键内相对较细的电子因子已显示出对光谱性质有深远影响，[CpFe（dmpe）（BOMes）]

  DOI：

  10.1016/j.jorganchem.2012.05.005

文献信息

• (Dimethylamino)borylene and Related Complexes of Electron-Rich Metal Fragments: Generation of Nucleophile-Resistant Cations by Spontaneous Halide Ejection
  作者：David A. Addy、Nicholas Phillips、Glesni A. Pierce、Dragoslav Vidovic、Tobias Krämer、Dibyendu Mallick、Eluvathingal D. Jemmis、Gill Reid、Simon Aldridge

  DOI：10.1021/om201144e

  日期：2012.2.13

  Spontaneous halide ejection from a three-coordinate Lewis acid has been shown to offer a remarkable new route to cationic metal complexes featuring a linear, multiply bonded boron-donor Ligand. The exploitation of electron-rich [CpM(PR3)(2)] fragments within boryl systems of the type LnMB(hal)NR2 leads to the spontaneous formation in polar solvents of chemically robust borylene complexes, [LnM(BNR2)](+), with exceptionally low electrophilicity and short M-B bonds. This is reflected by M-B distances (ca. 1.80 angstrom for FeB systems) which are more akin to alkyl-/aryl-substituted borylene complexes and, perhaps most strikingly, by the very low exothermicity associated with the binding of pyridine to the two-coordinate boron center (Delta H = -7.4 kcal mol(-1), cf. -40.7 kcal mol(-1) for BCl3). Despite the strong pi electron release from the metal fragment implied by this suppressed reactivity and by such short M-B bonds, the barrier to rotation about the Fe=B bond in the unsymmetrical variant [CpFe(dmpe)(BNC6H4OMe-4}Me)](+) is found to be very small (ca. 2.9 kcal mol(-1)). This apparent contradiction is rationalized by the orthogonal orientations of the HOMO and HOMO-2 orbitals of the [CpML2](+) fragment, which mean that the M-B pi interaction does not fall to zero even in the highest energy conformation.