[Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)](OTf) | 170424-04-1

• 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: [Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)](OTf)
• 英文别名: Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(OTf)
• CAS: 170424-04-1；170424-08-5
• 化学式: CF₃O₃S*C₁₄H₃₂N₄Ni
• 分子量: 464.195
• InChiKey: DFUVHEVCUYEUAZ-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：

  二乙基二硫醚 、 [Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)](OTf) 以 四氢呋喃 为溶剂， 生成 RSRS-[Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(SEt)]CF3SO3
  参考文献：
  名称：

  Syntheses, Reactivity and Molecular Structures of RSRS-[Ni(tmc)SC6H5](PF6), RRSS-[Ni(tmc)SC6H5](CF3SO3) and RRSS-[Ni(tmc)](CF3SO3) (tmc = 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane)

  摘要：

  The RSRS and RRSS isomers of [Ni(tmc)](OTf)2 (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; OTf(-) = CF3SO3-) react with NaSC6H5 to yield the corresponding high spin, five-coordinate derivatives, [Ni(tmc)SC6H5](OTf). The molecular structure of each has been determined by X-ray diffraction. RRSS-[Ni(tmc)SC6H5](OTf) crystallized in the monoclinic space group P2(1)/n, with a = 12.648(3) Angstrom, b = 15.145(4) Angstrom, c = 14.765(4) Angstrom, beta = 113.96(2)degrees, V = 2584(1) Angstrom(3), and Z = 4. The coordination sphere about Ni is best described as square pyramidal with a Ni-S bond distance of 2.369(2) Angstrom and Ni-N-av of 2.128 Angstrom. RSRS-[Ni(tmc)SC6H5]-(PF6) crystallized in the monoclinic space group P2(1)/n, with a = 13.037(5) Angstrom, b = 15.407(7) Angstrom, c = 13.706(7) Angstrom, beta = 113.53(3)degrees, V = 2524(2) Angstrom(3), and Z = 4. The Ni resides in a highly distorted square pyramid with a shorter Ni-S distance, 2.352(2)Angstrom and correspondingly longer Ni-N-av distance of 2.149 Angstrom. Alternatively [Ni(tmc)SR](OTf) may be produced by oxidative addition of disulfide, R(2)S(2) (R = C6H5, C2H5), to Ni(tmc)(OTf). The second-order rate constant, k(i), for reaction with (C6H5)(2)S-2 is 120 M(-1)s(-1). (C2H5)(2)S-2 reacts 5 orders of magnitude more slowly consistent with its greater S-S bond dissociation energy. The nickel thiolates react with haloalkanes, RX (RX = CH3I, C2H5I, (CH3)(2)CHI, C6H5CH2Cl), producing [Ni(tmc)X](OTf) and C(6)H(5)SR. The reaction is second order with k(2) decreasing in the order, CH3I > C2H5I > (CH3)(2)CHI. Strikingly, for reactions with a given RX, the RRSS isomer reacted ca. 350 times faster than the RSRS isomer. RRSS-[Ni(tmc)](OTf) Na(OTf) has also been characterized, having crystallized in the monoclinic space group C2/c, with a = 24.690(23) Angstrom, b = 11.261(5) Angstrom, c = 9.681(6) Angstrom, beta = 91.03(4)degrees, V = 2691(2) Angstrom(3), and Z = 4. The macrocycle provides the Ni(I) ion with a square planar coordination environment in which there are two distinct Ni-N bond distances, 2.120(5) and 2.095(5) Angstrom.

  DOI：

  10.1021/ic00127a029
• 作为产物：
  描述：

  {(R,R,S,S)1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane}nickel(II) bis(trifluoromethane sulfonate) 在 sodium amalgam 作用下， 以 乙腈 为溶剂， 生成 [Ni(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)](OTf)
  参考文献：
  名称：

  镍苄基配合物分解的动力学和机理以及镍苄基键解离能的测定

  摘要：

  摘要甲基辅酶M还原酶（MCR）包含方形平面镍planar素辅因子F 430，催化产甲烷古生菌甲烷生物合成的最后一步。关于该酶的最新机制建议表明，假定的有机镍中间体可能通过自由基途径发生反应。制备了使用1,4,8,11-四甲基-1,4,8,11-四氮杂环十四烷（tmc）的苄基镍配合物，并通过动力学方法确定了其均相NiC键解离能。在过量Ni（tmc）+存在下，NiCH2 Ph（tmc）+在乙腈中的分解动力学与镍苄基键的可逆均相反应，然后根据速率定律重新结合苄基相一致-d [NiCH2 Ph（tmc）+] / dt = k obs [NiCH2 Ph（tmc）+] 2，其中k obs = 2（k 4 2 k 5）/（k -4 2）[Ni（tmc）+] 2。根据活化参数（苄基：ΔH‡obs = 40.6±0.6 kcal mol -1，ΔS‡obs = 61.8±2.0 cal mol -1

  DOI：

  10.1016/s0020-1693(02)01349-x

文献信息

• Synthesis and Spectroscopic Identification of a μ-1,2-Disulfidodinickel Complex
  作者：Matthew T. Kieber-Emmons、Katherine M. Van Heuvelen、Thomas C. Brunold、Charles G. Riordan

  DOI：10.1021/ja807735a

  日期：2009.1.21

  Reduction of elemental sulfur by a monovalent nickel precursor leads to a trans-1,2-mu-disulfidodinickel(II) complex assigned based on a combination of advanced spectroscopic methods in conjunction with density functional theory calculations. The disulfido linkage is characterized by an intense optical S --> Ni charge transfer transition at 650 nm, which causes a significant distortion of the Ni(2)S(2)

  基于先进光谱方法结合密度泛函理论计算，通过单价镍前体还原元素硫产生反式 1,2-mu-二硫代二镍 (II) 络合物。二硫键的特点是在 650 nm 处发生强烈的光学 S --> Ni 电荷转移跃迁，这会导致 Ni(2)S(2) 核沿同位素敏感的 v(SS) 模式在 474 cm 处发生显着畸变(-1)，如该振动特征的共振拉曼激发曲线所示。