{Pri-Cl}-trans-{Co(rac-(1,8)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)(OH2)Cl}(ClO4)2 | 122742-54-5

• 英文名称: {Pri-Cl}-trans-{Co(rac-(1,8)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)(OH2)Cl}(ClO4)2
• CAS: 122742-54-5
• 化学式: C₁₆H₃₄ClCoN₄O*2ClO₄
• 分子量: 591.82
• InChiKey: XZLYRRJJKXULFN-PRNSBOFBSA-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：

  硫氰酸酯 、 {Pri-Cl}-trans-{Co(rac-(1,8)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)(OH2)Cl}(ClO4)2 以 not given 为溶剂， 生成 {trans-Co({Pri-Cl}-rac-(1,8)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-1,11-diene)(SCN)Cl}(1+)
  参考文献：
  名称：

  导致反式水甲基（四氮杂大环）钴（III）配合物不稳定的电子和立体化学因素。动力学和分子力学研究

  摘要：

  通过使用一系列反式-Co(N{sub 4})(OH{sub 2})CH{sub 3} 的阴离子反应研究了Co-烷基键的反式不稳定影响的起源和可变性{sup 2+}（N{sub 4} 是四氮杂大环配体）配合物作为探针。一些相关的反式 Co(N{sub 4})(OH{sub 2})Cl{sup 2+} 配合物的阴离子反应也已被检验，以提供与密切相关的经典配位配合物进行比较的基础。Co(N{sub 4})(OH{sub 2}){sub 2}{sup 2+}, Co(N{sub 4})(OH{sub 2})CH{sub 中置换的简单静电模型3}{sup 2+} 和 Co(N{sub 4})(OH{sub 2})Cl{sup 2+} 复合物表明对于在Co(Me{sub 6}(14)dieneN{sub 4})(OH{sub 2})CH{sub 3}{sup 2+} 的立体化学杂乱位点比整洁的位点。

  DOI：

  10.1021/ja00201a021
• 作为产物：
  描述：

  trans-dichloro(5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)cobalt(III)(ClO4) 在 高氯酸 作用下， 以 not given 为溶剂， 生成 {Pri-Cl}-trans-{Co(rac-(1,8)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)(OH2)Cl}(ClO4)2
  参考文献：
  名称：

  配位化合物的结构和机理研究。第18部分。反式-溴和氯氰基-（5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四碳-7,14-二烯）钴的制备和水解（III）阳离子

  摘要：

  配合物的反式- [CO（CN）（L 1）X] Ñ + [L 1 = 5,5,7,12,12,14六甲基-1,4,8,11-四- azacyclotetradeca- 7,14-二烯 已经制备了X ＝ Cl，Br或OH 2 ]和反式-[CoL 1（OH 2）（SO 3）] +，并且已经在一定温度范围内研究了卤代配合物的酸和碱水解。对于酸水解，氰基四胺钴的动力学数据之间建立了线性自由能关系（III）络合物以及相应的叠氮基和异硫氰酸氰基络合物的络合物。这些配合物的碱水解是在“限制”来讨论小号Ñ 1（CB）机构，其中反应性酰氨基共轭碱的形成是限速步骤。

  DOI：

  10.1039/dt9770001931

文献信息

• Schwarz, Carolyn L.; Endicott, John F., Inorganic Chemistry, 1989, vol. 28, # 21, p. 4011 - 4018
  作者：Schwarz, Carolyn L.、Endicott, John F.

  DOI：——

  日期：——
• Inner-Sphere Self-Exchange Electron Transfer in Low-Spin Co(III)-Co(II) Couples. Rate Determinations from 1H-NMR Line Broadening and a Simple Vibronic Model of the Reaction Coordinate
  作者：Carolyn L. Schwarz、John F. Endicott

  DOI：10.1021/ic00122a012

  日期：1995.8

  Inner-sphere electron transfer self-exchange rate constants have been determined using H-1-NMR line broadening for several low-spin Co(III)-Co(II) couples of the type Co(MCL)(OH2)X(2+)-Co(MCL)(OH2)(2)(2+), where MCL = a tetraazamacrocycle coordinated equatorially and X = Cl, Br, or N-3. This work confirms previous inferences, based mostly on cross-reaction data, that (1) the inner-sphere rate constants are about 10(6) times larger than the equivalent outer-sphere rate constants and (2) variations of some of the inner-sphere rate constants (at least those with X = Cl) parallel differences in reactant and product molecular structure but (3) the inner-sphere rate constants are much less sensitive to structural variations than are the equivalent outer-sphere rate constants. The characteristically smaller inner-sphere nuclear reorganizational barrier can be attributed in part to correlation of the Co(III)-X(-) stretch and the X(-)-Co(II) compression, and this suggests that electron transfer occurs in concert with the motion of the bridging ligand. A simple vibronic model is proposed to accommodate this concerted motion of the bridging ligand and the very strong donor-acceptor coupling in these systems. This model suggests that the nuclear reorganizational parameters for inner-sphere cross-reactions will not be averages of those of the self-exchange reaction components if electron transfer is accompanied by large nuclear displacements and if the bridging ligand is comparable in mass to the donor and acceptor. Further implications of this model for strong vibronic coupling are the lack of Marcus-inverted region behavior and variations of inner-sphere self-exchange rate constants with the mass of the bridging ligand.