CoN2(tris-(o-diisopropylphosphinophenyl)silyl) | 1130050-41-7

• 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-diisopropylphosphinophenyl)silyl)
• 英文别名: [((2-(i-Pr)2PC6H4)3Si)Co(N2)]；[(tris(o-(diisopropylphosphino)phenyl)silyl)Co(N2)]
• CAS: 1130050-41-7
• 化学式: C₃₆H₅₄CoN₂P₃Si
• 分子量: 694.838
• InChiKey: ONMKQKWZJUHZPD-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：

  CoN2(tris-(o-diisopropylphosphinophenyl)silyl) 、 氢气 以 氘代甲苯 为溶剂， 反应 120.0h， 生成 CoH2(tris-(o-diisopropylphosphinophenyl)silyl)
  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：

  [((2-(i-Pr)2PC6H4)3Si)Co(PMe3)][tetrakis(3,5-bis(trifluoromethyl)phenyl)borate] 、 氮气 在 [Co(C₅Me₅)2] 作用下， 以 not given 为溶剂， 以99%的产率得到CoN2(tris-(o-diisopropylphosphinophenyl)silyl)
  参考文献：
  名称：

  A Homologous Series of Cobalt, Rhodium, and Iridium Metalloradicals

  摘要：

  We herein present a series of d(7) trirnethyl-phosphine complexes of group 9 metals that are chelated by the tripodal tetradentate tris(phosphino)silyl ligand [SiP(3)(iPr)]H ([SiP(3)(iPr)] = (2-iPr(2)PC(6)H(4))(3)Si(-)). Both electron paramagnetic resonance (EPR) simulations and density functional theory (DFT) calculations indicate largely metalloradical character. These complexes provide a rare opportunity to compare the properties between the low-valent metalloradicals of the second- and third-row transition metals with the corresponding first-row analogues.

  DOI：

  10.1021/ic202079r

文献信息

• Dinitrogen Complexes Supported by Tris(phosphino)silyl Ligands
  作者：Matthew T. Whited、Neal P. Mankad、Yunho Lee、Paul F. Oblad、Jonas C. Peters

  DOI：10.1021/ic801855y

  日期：2009.3.16

  [Si(o-C6H4PiPr2)3]−) has been prepared, and its complexation with iron, cobalt, nickel, and iridium precursors has been explored. Several coordination complexes have been thoroughly characterized and are described. These include, for example, the divalent trigonal bipyramidal metal chlorides [SiPiPr3]M−Cl (M = Fe, Co, Ni), as well as the monovalent dinitrogen adducts [SiPiPr3]M−N2 (M = Fe, Co, Ir), which are

  制备了四齿三（膦）甲硅烷基配体[SiP i Pr 3 ]（[SiP i Pr 3 ] = [Si（o -C 6 H 4 P i Pr 2）3 ] -），并与铁络合，已经研究了钴，镍和铱的前体。几种配位配合物已被彻底表征和描述。这些包括，例如，二价三角双锥体金属氯化物[SiP i Pr 3 ] M-Cl（M = Fe，Co，Ni），以及一价二氮加合物[SiP i Pr 3 ] M-N2（M = Fe，Co，Ir），与相关的[SiP Ph 3 ] M-Cl和[SiP Ph 3 ] M-N 2种类（M = Fe，Co）进行比较。这种类型的络合物代表单价铁的末端二氮加合物的第一个实例，并且配体结构允许用经转位的甲硅烷基供体检查独特种类的二氮加合物。适当的[SiP R 3 ] M-N 2前体的氧化得到二价三氟甲磺酸铁[SiP Ph 3 ] Fe（OTf）和三价三氟甲磺酸钴[SiP i Pr 3] Co（OTf）}