[Mn(CO)(dppe)2][B(C6H3(3,5-CF3)2)4] | 178318-15-5

• 英文名称: [Mn(CO)(dppe)2][B(C6H3(3,5-CF3)2)4]
• CAS: 178318-15-5
• 化学式: C₃₂H₁₂BF₂₄*C₅₃H₄₈MnOP₄
• 分子量: 1743.02
• InChiKey: KSLUMBOCPDXBTN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Mn(CO)(dppe)2][B(C6H3(3,5-CF3)2)4] 、 15N-氨 以 氟苯 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  从Mn–NH 3络合物中夺取三次氢原子会产生环磷氮鎓阳离子†

  摘要：

  的NH的氢原子全部3中[锰（DEPE）2（CO）（NH 3）] +通过抽象-2,4,6-三-叔-butylphenoxyl自由基，导致罕见cyclophosphazenium阳离子的分离，[ （Et 2 P（CH 2）2 PEt 2）N] +，产率为76％。对于[Mn（dppe）2（CO）（NH 3）] +观察到类似的反应。计算表明，将NH x插入Mn-P键可提供热力学驱动力。该反应的背景信息化提供了关于催化剂设计和打破牢固的NH键的见解。

  DOI：

  10.1039/c9cc06915a
• 作为产物：
  描述：

  Mn(1,2-bis(diphenylphosphino)ethane)2(CO)(Br) 、 四(3,5-二(三氟甲基)苯基)硼酸钠 以 二氯甲烷 为溶剂， 生成 [Mn(CO)(dppe)2][B(C6H3(3,5-CF3)2)4]
  参考文献：
  名称：

  阳离子锰 (I) 二氢和二氮配合物，衍生自具有双极性相互作用的正式 16 电子配合物，[Mn(CO)(Ph2PC2H4PPh2)2]+

  摘要：

  我们合成了一种新的 16 电子前体 [Mn(CO)(dppe){sub 2}]BAr`{sub 4} (1) 能够结合小分子 (dppe = Ph{sub 2}PC{sub 2}H {sub 4}PPh{sub 2}; BAr`{sub 4} = B[C{sub 6}H{sub 3}(3,5-CF{sub 3}){sub 2}]{sub 4}) . 该物种产生了第一个表征良好的阳离子锰-H{sub 2} 复合物，[Mn(H{sub 2})(CO)(dppe){sub 2}]BAr`{sub 4}。提出复合物 MnH{sub 3}(R{sub 2}PC{sub 2}H{sub 4}PR{sub 2}){sub 2} [R = Me (dmpe), Et (depe)] H{sub 2} 配体和 CpMn(CO){sub 2}(H{sub 2}) 最近被分离出来。我们还报告说，N{sub 2}

  DOI：

  10.1021/ja960499q

文献信息

• Reversible Displacement of Polyagostic Interactions in 16e [Mn(CO)(R₂PC₂H₄PR₂)₂]⁺ by H₂, N₂, and SO₂. Binding and Activation of η²-H₂ trans to CO Is Nearly Invariant to Changes in Charge and cis Ligands
  作者：Wayne A. King、Brian L. Scott、Juergen Eckert、Gregory J. Kubas

  DOI：10.1021/ic981263l

  日期：1999.3.1

  Electrophilic 16e [Mn(CO)(R2PC2H4PR2)(2)](+) complexes (R = Et, Ph) are synthesized by metathesis of MnBr(CO)(R2PC2H4PR2)(2) with Na or Li salts of low-coordinating baron or gallium anions (e.g., [BC6H3(3,5-CF3)(2)}(4)](-) or [Ga(C6F5)(4)](-)). They contain weak polyagostic interactions that are reversibly displaced by H-2, N-2, and SO2 (which is a surprisingly weak ligand here). The agostic aid H-2 complexes, as well as the gallium anions including the new species [Ga(C6F5)(3)}(2)(mu-Cl)](-), have been characterized by NMR, IR, and X-ray crystallography. The agostic Mn-H distances (e.g., 2.9 Angstrom) are much longer than those found for the single agostic interactions in Mo(CO)(diphosphine)(2) and [Mn(CO)(3)(PCy3)(2)](+). The H-H and also the Mn-H distances have been determined in the H-2 complex by T-1 measurements for both the H-2 and HD isotopomers. IR data and C-O and M-C bond lengths are used to gauge the pi-acceptor strengths of ligands trans to the CO. The agostic C-H bonds are the weakest ligands and also the weakest accepters, but the H-2 ligand is an excellent acceptor as strong as N-2 and ethylene. The variation of nu(CO) on increasing the basicity of the cis-phosphine (dppe versus depe) in trans-M(CO)(diphosphine)(2)(L) is less than expected and far less than that on increasing the charge on the complex (M = Mn+ versus Mo). The H-H bond lengths (0.87-0.90 Angstrom) and J(HD) NMR couplings (32-34 Hz) in [Mn(CO)(R2PC2H4PR2)(2)(H-2)](+) and other cationic H-2 complexes with trans-CO are strikingly similar to their neutral analogues and nearly invariant. Activation of H-H in the more electrophilic cationic systems occurs primarily via increased a donation from H-2 as compared to the more electron-rich neutral analogues where back-bonding dominates. The nature of the ligand trans to H-2 (the strong acceptor CO here) controls the H-H distance more so than all of the cis ligands combined, especially fbr cationic complexes.