((C6F5NCH2CH2)3N)MoOTf | 155019-65-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: ((C6F5NCH2CH2)3N)MoOTf
• CAS: 155019-65-1
• 化学式: C₂₅H₁₂F₁₈MoN₄O₃S
• 分子量: 886.373
• InChiKey: LITUMYDVXWEXIR-UHFFFAOYSA-M

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：

  ((C6F5NCH2CH2)3N)MoOTf 在 Na#Hg 、 N₂ 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Synthesis of Molybdenum and Tungsten Complexes That Contain Triamidoamine Ligands of the Type (C6F5NCH2CH2)3N and Activation of Dinitrogen by Molybdenum

  摘要：

  Three new ligands of the type (ArNHCH2CH2)(3)N (Ar = 3,5-bis(trifluoromethyl)phenyl, 2-(trifluoromethyl)phenyl, and pentafluorophenyl) have been prepared. Only Mo and W complexes containing the [(C6F5NCH2CH2)(3)N](3-) ([N3N](3-)) ligand were found to be stable. Stable complexes that have been prepared include Mo[N3N](NMe(2)), M[N3N]Cl(M = Mo or W), Mo[N3N](OTf) (M = Mo or W), [N3N]M=N (M = Mo or W), and {[N3N]Mo=NMe}(OTf). An X-ray study of Mo[N3N]Cl showed it to be a monomeric distorted trigonal bipyramidal species having a pseudo-C-3 symmetry (space group P (1) over bar, a = 11.265(2) Angstrom, b = 11.371(2) Angstrom, c = 21.805(4) Angstrom, alpha = 82.40(1)degrees, beta = 79.07(1)degrees, gamma = 74.89(1)degrees, V = 2637.4 Angstrom(3), Z = 4, fw = 772.75, rho(calcd) = 1.946 g/cm(3), R = 0.032, R(W) = 0.034). Reduction of Mo[N3N](OTf) with 1 equiv of sodium amalgam yields a dinuclear bridging dinitrogen species, [N3N]Mo(mu N-2)Mo[N3N]. In the presence of 2 equiv of sodium amalgam in ether Mo[N3N](OTf) is reduced to [N3N]Mo(N-2)[Na(ether)(x)] (1 < x < 2). A more stable 15-crown-5 derivative can be prepared and more fully characterized. [N3N]Mo(mu-N-2)Mo[N3N] can be reduced to [N3N]Mo(N-2)[NaL(x)] by sodium amalgam under dinitrogen and the latter can be oxidized to the former by ferrocenium triflate or air. [N3N]Mo(N-2)[NaL(x)] reacts with Mo[N3N](OTf) to give [N3N]Mo(mu-N-2)Mo[N3N], with triisopropylsilyl chloride to give [N3N]MoN=NSi(i-Pr)(3), and with tributyltin chloride to give [N3N]MoN=NSn(Bu)(3). An X-ray study of [N3N]MoN=NSi(i-Pr)(3) (space group P2(1)/n, a 13.524(3) Angstrom, b = 18.016(4) Angstrom, c = 16.248(3) Angstrom, beta = 98.74(2)degrees, V = 3913(1) Angstrom(3), Z = 4, fw = 922.67, rho(calcd) = 1.566 g/cm(3), R = 0.069, R(W) = 0.072) showed it to be a trigonal bipyramidal complex containing a slightly bent diazenido ligand (Mo-N-alpha = 1.788(9) Angstrom, Mo-N-alpha-N-beta = 171.1(8)degrees, N-alpha-N-beta-Si = 154(1)degrees).

  DOI：

  10.1021/ja00089a028
• 作为产物：
  描述：

  在 ferrocenium triflate 作用下， 以 二氯甲烷 为溶剂， 生成 ((C6F5NCH2CH2)3N)MoOTf
  参考文献：
  名称：

  Synthesis of Molybdenum and Tungsten Complexes That Contain Triamidoamine Ligands of the Type (C6F5NCH2CH2)3N and Activation of Dinitrogen by Molybdenum

  摘要：

  Three new ligands of the type (ArNHCH2CH2)(3)N (Ar = 3,5-bis(trifluoromethyl)phenyl, 2-(trifluoromethyl)phenyl, and pentafluorophenyl) have been prepared. Only Mo and W complexes containing the [(C6F5NCH2CH2)(3)N](3-) ([N3N](3-)) ligand were found to be stable. Stable complexes that have been prepared include Mo[N3N](NMe(2)), M[N3N]Cl(M = Mo or W), Mo[N3N](OTf) (M = Mo or W), [N3N]M=N (M = Mo or W), and {[N3N]Mo=NMe}(OTf). An X-ray study of Mo[N3N]Cl showed it to be a monomeric distorted trigonal bipyramidal species having a pseudo-C-3 symmetry (space group P (1) over bar, a = 11.265(2) Angstrom, b = 11.371(2) Angstrom, c = 21.805(4) Angstrom, alpha = 82.40(1)degrees, beta = 79.07(1)degrees, gamma = 74.89(1)degrees, V = 2637.4 Angstrom(3), Z = 4, fw = 772.75, rho(calcd) = 1.946 g/cm(3), R = 0.032, R(W) = 0.034). Reduction of Mo[N3N](OTf) with 1 equiv of sodium amalgam yields a dinuclear bridging dinitrogen species, [N3N]Mo(mu N-2)Mo[N3N]. In the presence of 2 equiv of sodium amalgam in ether Mo[N3N](OTf) is reduced to [N3N]Mo(N-2)[Na(ether)(x)] (1 < x < 2). A more stable 15-crown-5 derivative can be prepared and more fully characterized. [N3N]Mo(mu-N-2)Mo[N3N] can be reduced to [N3N]Mo(N-2)[NaL(x)] by sodium amalgam under dinitrogen and the latter can be oxidized to the former by ferrocenium triflate or air. [N3N]Mo(N-2)[NaL(x)] reacts with Mo[N3N](OTf) to give [N3N]Mo(mu-N-2)Mo[N3N], with triisopropylsilyl chloride to give [N3N]MoN=NSi(i-Pr)(3), and with tributyltin chloride to give [N3N]MoN=NSn(Bu)(3). An X-ray study of [N3N]MoN=NSi(i-Pr)(3) (space group P2(1)/n, a 13.524(3) Angstrom, b = 18.016(4) Angstrom, c = 16.248(3) Angstrom, beta = 98.74(2)degrees, V = 3913(1) Angstrom(3), Z = 4, fw = 922.67, rho(calcd) = 1.566 g/cm(3), R = 0.069, R(W) = 0.072) showed it to be a trigonal bipyramidal complex containing a slightly bent diazenido ligand (Mo-N-alpha = 1.788(9) Angstrom, Mo-N-alpha-N-beta = 171.1(8)degrees, N-alpha-N-beta-Si = 154(1)degrees).

  DOI：

  10.1021/ja00089a028

文献信息

• Synthesis, Structure, and Electrochemical Studies of Molybdenum and Tungsten Dinitrogen, Diazenido, and Hydrazido Complexes That Contain Aryl-Substituted Triamidoamine Ligands
  作者：George E. Greco、Richard R. Schrock

  DOI：10.1021/ic001123n

  日期：2001.7.1

  include ([t-BuC(6)H(4)N(3)N]Mo)(2)(N(2)), Na(THF)(6)([PhN(3)N]Mo-N=N)(2)Na(THF)(3), [t-BuC(6)H(4)N(3)N]Mo-N=N-Na(15-crown-5), and ([Ph(2)C(6)H(3)N(3)N]MoNN)(2)Mg(DME)(2). Compounds of the type [ArN(3)N]Mo-N=N-Mo[ArN(3)N] do not appear to form when Ar = 3,5-Ph(2)C(6)H(3) or 3,5-(4-t-BuC(6)H(4))(2)C(6)H(3), presumably for steric reasons. Treatment of diazenido complexes (e.g., [ArN(3)N]Mo-N=N-Na(THF)(x))

  单电子还原[ArN（3）N] MoCl络合物（Ar = C（6）H（5），4-FC（6）H（4），4-t-BuC（6）H（4）， 3,5-Me（2）C（6）H（3））产生[ArN（3）N] Mo-N = N-Mo [ArN（3）N]类型的配合物，而两电子还原产生（[ArN（3）N] Mo-N = N）（-）衍生物（Ar = C（6）H（5），4-FC（6）H（4），4-t-BuC（6）H （4），3,5-Me（2）C（6）H（3），3,5-Ph（2）C（6）H（3）和3,5-（4-t-BuC（ 6）H（4））（2）C（6）H（3））。晶体学表征的化合物包括[[t-BuC（6）H（4）N（3）N] Mo）（2）（N（2）），Na（THF）（6）（[PhN（3）N ] Mo-N = N）（2）Na（THF）（3），[t-BuC（6）H（4）N（3）N] Mo-N = N-Na（15-crown
• Synthesis of [(Me₃SiNCH₂CH₂)₃N]³^- and [(C₆F₅NCH₂CH₂)₃N]³^- Complexes of Molybdenum and Tungsten That Contain CO, Isocyanides, or Ethylene
  作者：George E. Greco、Myra B. O'Donoghue、Scott W. Seidel、William M. Davis、Richard R. Schrock

  DOI：10.1021/om990748u

  日期：2000.3.1

  Paramagnetic complexes of the type [N3N]MoL ([N3N](3-) = [(Me3SiNCH2CH2)(3)N](3-); L = CO, RNC, C2H4) have been prepared by displacing dinitrogen from [N3N]Mo(N-2). [N3N]Mo(CO) was reduced by magnesium powder in the presence of Me3SiCl to yield the diamagnetic oxycarbyne complex [N3N]Mo=COSiMe3, while oxidation of [N3N]Mo(CN-t-Bu) with [Cp2Fe]OTf yielded [N3N]Mo(CN-t-Bu)}OTf. Thermolysis of [N3N]Mo(CN-t-Bu) resulted in loss of a t-Bu radical to yield [N3N]Mo(CN), which was structurally characterized, [N3NFML ([N3NF](3-) = [(C6F5NCH2CH2)(3)N](3-) M = Mo, W; L = CO, RNC) complexes have been prepared by one-electron reduction of [N3NF]M(OTf) in the presence of L. An X-ray study of [N3NF]W(CN-t-Bu) showed it to contain a bend isocyanide ligand. Anionic CO complexes were prepared by the two-electron reduction of [N3NF]M(OTf) in the presence of CO. An X-ray study of [N3NF]W(CO)(2)}Na(ether)(3) revealed it to have a pseudo-octahedral structure in which sodium is bound to the CO trans tb the amine donor atom. Treatment of [N3NF]M(CO)}(-) complexes with Me3SiCl gave oxycarbyne complexes [N3NF]M=COSiMe3. Reaction of [N3NF]WCO with V(Mes)(3)(THF) yielded [N3NF]W(CO)V(Mes)(3), the structure of which was determined in an X-ray study. Cationic [N3NF](3-) complexes could be prepared that contain up to 3 equiv of isocyanide. An X-ray study of [N3NF]W(CN-t-Bu)(3)}BPh4 showed it to be a seven-coordinate species with one isocyanide located in the equatorial plane and the other two isocyanide ligands in the apical pocket. Reduction of [N3NF]W(OTf) under ethylene gave [N3NF]W(C2H4), which could be oxidized to yield diamagnetic [N3NF]W(C2H4)}OTf.