CoN2(tris-(o-diisopropylphophinophenyl)borane) | 1393890-41-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: CoN2(tris-(o-diisopropylphophinophenyl)borane)
• 英文别名: (TPB)Co(N₂)；[2-bis[2-di(propan-2-yl)phosphanylphenyl]boranylphenyl]-di(propan-2-yl)phosphane;cobalt;molecular nitrogen
• CAS: 1393890-41-9
• 化学式: C₃₆H₅₄BCoN₂P₃
• 分子量: 677.564
• InChiKey: RXCWJAJQLVUCIS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.0
• 重原子数：
  43
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  CoN2(tris-(o-diisopropylphophinophenyl)borane) 以 氘代苯 为溶剂， 生成 [2-bis[2-di(propan-2-yl)phosphanylphenyl]boranylphenyl]-di(propan-2-yl)phosphane;cobalt
  参考文献：
  名称：

  Dihydrogen Binding to Isostructural S = ¹/₂ and S = 0 Cobalt Complexes

  摘要：

  Two isostructural, nonclassical Co(H(2)) complexes are prepared from their Co(N(2)) precursors using tris(phosphino)silyl and tris(phosphino)borane ancillary ligands. Comproportionation of CoBr(2) and Co metal in the presence of TPB (tris-(o-diisopropylphophinophenyl)borane) gives (TPB)CoBr (4). One-electron reduction of 4 triggers N(2) binding to give (TPB)Co(N(2)) (2-N(2)) which is isostructural to previously reported [SiP(3)]Co(N(2)) (1-N(2)) ([SiP(3)] = tris-(o-diisopropylphosphinophenyl)silyl). Both 1-N(2) and 2-N(2) react with 1 atm H(2) to generate thermally stable H(2) complexes 1-H(2) and 2-H(2), respectively. Both complexes are characterized by a suite of spectroscopic techniques in solution and by X-ray crystallography. The H(2) and N(2) ligands in 2-H(2) and 2-N(2) are labile under ambient conditions and the binding equilibria are observable by temperature-dependent UV/vis. A van't Hoff analysis allows for the ligand binding energetics to be determined (H(2): ΔH(o) = -12.5(3) kcal mol(-1) and ΔS(o) = -26(3) cal K(-1) mol(-1); N(2): ΔH(o) = -13.9(7) kcal mol(-1) and ΔS(o) = -32(5) cal K(-1) mol(-1)).

  DOI：

  10.1021/ja305248f
• 作为产物：
  描述：

  CoBr(tris-(o-diisopropylphophinophenyl)borane) 、 氮 在 sodium naphthalenide 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以76%的产率得到CoN2(tris-(o-diisopropylphophinophenyl)borane)
  参考文献：
  名称：

  Dihydrogen Binding to Isostructural S = ¹/₂ and S = 0 Cobalt Complexes

  摘要：

  Two isostructural, nonclassical Co(H(2)) complexes are prepared from their Co(N(2)) precursors using tris(phosphino)silyl and tris(phosphino)borane ancillary ligands. Comproportionation of CoBr(2) and Co metal in the presence of TPB (tris-(o-diisopropylphophinophenyl)borane) gives (TPB)CoBr (4). One-electron reduction of 4 triggers N(2) binding to give (TPB)Co(N(2)) (2-N(2)) which is isostructural to previously reported [SiP(3)]Co(N(2)) (1-N(2)) ([SiP(3)] = tris-(o-diisopropylphosphinophenyl)silyl). Both 1-N(2) and 2-N(2) react with 1 atm H(2) to generate thermally stable H(2) complexes 1-H(2) and 2-H(2), respectively. Both complexes are characterized by a suite of spectroscopic techniques in solution and by X-ray crystallography. The H(2) and N(2) ligands in 2-H(2) and 2-N(2) are labile under ambient conditions and the binding equilibria are observable by temperature-dependent UV/vis. A van't Hoff analysis allows for the ligand binding energetics to be determined (H(2): ΔH(o) = -12.5(3) kcal mol(-1) and ΔS(o) = -26(3) cal K(-1) mol(-1); N(2): ΔH(o) = -13.9(7) kcal mol(-1) and ΔS(o) = -32(5) cal K(-1) mol(-1)).

  DOI：

  10.1021/ja305248f

文献信息

• Evaluating Molecular Cobalt Complexes for the Conversion of N₂ to NH₃
  作者：Trevor J. Del Castillo、Niklas B. Thompson、Daniel L. M. Suess、Gaël Ung、Jonas C. Peters

  DOI：10.1021/acs.inorgchem.5b00645

  日期：2015.10.5

  Well-defined molecular catalysts for the reduction of N-2 to NH3 with protons and electrons remain very rare despite decades of interest and are currently limited to systems featuring molybdenum or iron. This report details the synthesis of a molecular cobalt complex that generates superstoichiometric yields of NH3 (>200% NH3 per Co-N-2 precursor) via the direct reduction of N-2 with protons and electrons. While the NH3 yields reported herein are modest by comparison to those of previously described iron and molybdenum systems, they intimate that other metals are likely to be viable as molecular N, reduction catalysts. Additionally, a comparison of the featured tris(phosphine)borane Co-N-2 complex with structurally related Co-N-2 and Fe-N-2 species shows how remarkably sensitive the N, reduction performance of potential precatalysts is. These studies enable consideration of the structural and electronic effects that are likely relevant to N-2 conversion activity, including the pi basicity, charge state, and geometric flexibility.