| 1536255-80-7

• CAS: 1536255-80-7
• 化学式: C₃₉H₄₁Cl₂MnN₃P₂
• 分子量: 739.566
• InChiKey: GZFSPJWKWHFWLT-IUUXVKSRSA-L

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：

  在 cyclooctatetraene 、 sodium 、 汞 作用下， 以 四氢呋喃 为溶剂， 以47%的产率得到C₃₉H₄₁MnN₃P₂
  参考文献：
  名称：

  A Highly Active Manganese Precatalyst for the Hydrosilylation of Ketones and Esters

  摘要：

  The reduction of ((PDI)-P-Ph2PPr)MnCl2 allowed the preparation of the formally zerovalent complex, ((PDI)-P-Ph2PPr)Mn, which features a pentadentate bis(imino)pyridine chelate. This complex is a highly active precatalyst for the hydrosilylation of ketones, exhibiting TOFs of up to 76,800 h(-1) in the absence of solvent. Loadings as low as 0.01 mol % were employed, and ((PDI)-P-Ph2PPr)Mn was found to mediate the atom-efficient utilization of Si-H bonds to form quaternary silane products. ((PDI)-P-Ph2PPr)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. Electronic structure investigation of ((PDI)-P-Ph2PPr)Mn revealed that this complex possesses an unpaired electron on the metal center, rendering it likely that catalysis takes place following electron transfer to the incoming carbonyl substituent.

  DOI：

  10.1021/ja4116346
• 作为产物：
  描述：

  ^Ph2PPrPDI 、 MnCl2(tetrahydrofuran)1.5 以 甲苯 为溶剂， 反应 48.0h， 以93%的产率得到
  参考文献：
  名称：

  A Highly Active Manganese Precatalyst for the Hydrosilylation of Ketones and Esters

  摘要：

  The reduction of ((PDI)-P-Ph2PPr)MnCl2 allowed the preparation of the formally zerovalent complex, ((PDI)-P-Ph2PPr)Mn, which features a pentadentate bis(imino)pyridine chelate. This complex is a highly active precatalyst for the hydrosilylation of ketones, exhibiting TOFs of up to 76,800 h(-1) in the absence of solvent. Loadings as low as 0.01 mol % were employed, and ((PDI)-P-Ph2PPr)Mn was found to mediate the atom-efficient utilization of Si-H bonds to form quaternary silane products. ((PDI)-P-Ph2PPr)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. Electronic structure investigation of ((PDI)-P-Ph2PPr)Mn revealed that this complex possesses an unpaired electron on the metal center, rendering it likely that catalysis takes place following electron transfer to the incoming carbonyl substituent.

  DOI：

  10.1021/ja4116346

文献信息

• Mechanistic Investigation of Bis(imino)pyridine Manganese Catalyzed Carbonyl and Carboxylate Hydrosilylation
  作者：Tufan K. Mukhopadhyay、Christopher L. Rock、Mannkyu Hong、Daniel C. Ashley、Thomas L. Groy、Mu-Hyun Baik、Ryan J. Trovitch

  DOI：10.1021/jacs.7b00879

  日期：2017.4.5

  recently reported a bis(imino)pyridine (or pyridine diimine, PDI) manganese precatalyst, (Ph2PPrPDI)Mn (1), that is active for the hydrosilylation of ketones and dihydrosilylation of esters. In this contribution, we reveal an expanded scope for 1-mediated hydrosilylation and propose two different mechanisms through which catalysis is achieved. Aldehyde hydrosilylation turnover frequencies (TOFs) of

  我们最近报道了一种双（亚氨基）吡啶（或吡啶二亚胺，PDI）锰预催化剂，(Ph2PPrPDI)Mn (1)，它对酮的氢化硅烷化和酯的二氢硅烷化具有活性。在这项贡献中，我们揭示了 1 介导的氢化硅烷化的扩展范围，并提出了两种不同的催化机制。已经实现了高达 4900 min-1 的醛氢化硅烷化转换频率 (TOF)，这是第一行金属催化羰基氢化硅烷化报告的最高值。此外，1 已显示介导甲酸二氢硅烷化，前导 TOF 可达 330 min-1。在化学计量和催化条件下，发现将 PhSiH3 添加到 (Ph2PPrPDI)Mn 中会导致部分转化为新的抗磁性氢化物。通过将 NaEt3BH 添加到 (Ph2PPrPDI)MnCl2 中，实现了 (Ph2PPrPDI)MnH (2) 的独立制备，单晶 X 射线衍射分析表明该复合物具有封闭的三角双锥体固态几何形状。当 2,2,2-三氟苯乙酮加入到 1 中时，自由基转移产生