SIPr*NesCNO | 1332866-78-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: SIPr*NesCNO
• 英文别名: 1,3-Bis[2,6-di(propan-2-yl)phenyl]-2-[nitroso-(2,4,6-trimethylphenyl)methylidene]imidazolidine；1,3-bis[2,6-di(propan-2-yl)phenyl]-2-[nitroso-(2,4,6-trimethylphenyl)methylidene]imidazolidine
• CAS: 1332866-78-0
• 化学式: C₃₇H₄₉N₃O
• 分子量: 551.816
• InChiKey: WCBQBHFRUFBUGC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.5
• 重原子数：
  41
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  35.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [Mo(P)[N(tert-butyl)(3,5-dimethylphenyl)]3] 、 SIPr*NesCNO 以 氘代苯 为溶剂， 生成 (OP)Mo(N[t-Bu]-3,5-Me2C6H3)3
  参考文献：
  名称：

  Thermodynamic, Kinetic, and Mechanistic Study of Oxygen Atom Transfer from Mesityl Nitrile Oxide to Phosphines and to a Terminal Metal Phosphido Complex

  摘要：

  The enthalpies of oxygen atom transfer (OAT) from mesityl nitrile oxide (MesCNO) to Me3P, Cy3P, Ph3P, and the complex (Ar[Bu-t]N)(3)MoP (Ar = 3,5-C6H3Me2) have been measured by solution calorimetry yielding the following P-O bond dissociation enthalpy estimates in toluene solution (+/- 3 kcal mol(-1)): Me3PO [138.5], Cy3PO [137.6], Ph3PO [132.2], (Ar[Bu-t]N)(3)MoPO [108.9]. The data for (Ar[Bu-t]N)(3)MoPO yield an estimate of 60.2 kcal mol(-1) for dissociation of PO from (Ar[Bu-t]N)(3)MoPO. The mechanism of OAT from MesCNO to R3P and (Ar[Bu-t]N)(3)MoP has been investigated by UV-vis and FTIR kinetic studies as well as computationally. Reactivity of R3P and (Ar[Bu-t]N)(3)MoP with MesCNO is proposed to occur by nucleophilic attack by the lone pair of electrons on the phosphine or phosphide to the electrophilic C atom of MesCNO forming an adduct rather than direct attack at the terminal O. This mechanism is supported by computational studies. In addition, reaction of the N-heterocyclic carbene SIPr (SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene) with MesCNO results in formation of a stable adduct in which the lone pair of the carbene attacks the C atom of MesCNO. The crystal structure of the blue SIPr center dot MesCNO adduct is reported, and resembles one of the computed structures for attack of the lone pair of electrons of Me3P on the C atom of MesCNO. Furthermore, this adduct in which the electrophilic C atom of MesCNO is blocked by coordination to the NHC does not undergo OAT with R3P. However, it does undergo rapid OAT with coordinatively unsaturated metal complexes such as (Ar[Bu-t]N)(3)V since these proceed by attack of the unblocked terminal O site of the SIPr center dot MesCNO adduct rather than at the blocked C site. OAT from MesCNO to pyridine, tetrahydrothiophene, and (Ar[Bu-t]N)(3)MoN was found not to proceed in spite of thermochemical favorability.

  DOI：

  10.1021/ic2013599
• 作为产物：
  描述：

  2,4,6-三甲基苯甲腈N-氧化物 、 1,3-双(2,6-二异丙苯基)咪唑啉酮-2-亚基 以 氘代苯 为溶剂， 生成 SIPr*NesCNO
  参考文献：
  名称：

  Synthesis, structure, and thermochemistry of adduct formation between N-heterocyclic carbenes and isocyanates or mesitylnitrile oxide

  摘要：

  N-heterocyclic carbenes（NHC）与异氰酸酯反应后，在甲苯溶液中产生了稳定的齐聚亚胺酸盐/酰胺酸盐。对这些化合物进行了全面表征，并通过 X 射线晶体学确定了几种化合物的晶体结构。通过溶液量热法研究了这些化合物和相关化合物的结合热化学。比较了 NHC 与异氰酸酯 (RNCO) 和异构腈氧化物 (RCNO) 以及 CO2 的结合焓。此外，还进行了 DFT 计算，以进一步评估这些化合物的键合性质。

  DOI：

  10.1007/s11224-013-0305-2

文献信息

• Thermodynamic, Kinetic, and Mechanistic Study of Oxygen Atom Transfer from Mesityl Nitrile Oxide to Phosphines and to a Terminal Metal Phosphido Complex
  作者：Xiaochen Cai、Subhojit Majumdar、George C. Fortman、Luis Manuel Frutos、Manuel Temprado、Christopher R. Clough、Christopher C. Cummins、Meaghan E. Germain、Taryn Palluccio、Elena V. Rybak-Akimova、Burjor Captain、Carl D. Hoff

  DOI：10.1021/ic2013599

  日期：2011.10.3

  The enthalpies of oxygen atom transfer (OAT) from mesityl nitrile oxide (MesCNO) to Me3P, Cy3P, Ph3P, and the complex (Ar[Bu-t]N)(3)MoP (Ar = 3,5-C6H3Me2) have been measured by solution calorimetry yielding the following P-O bond dissociation enthalpy estimates in toluene solution (+/- 3 kcal mol(-1)): Me3PO [138.5], Cy3PO [137.6], Ph3PO [132.2], (Ar[Bu-t]N)(3)MoPO [108.9]. The data for (Ar[Bu-t]N)(3)MoPO yield an estimate of 60.2 kcal mol(-1) for dissociation of PO from (Ar[Bu-t]N)(3)MoPO. The mechanism of OAT from MesCNO to R3P and (Ar[Bu-t]N)(3)MoP has been investigated by UV-vis and FTIR kinetic studies as well as computationally. Reactivity of R3P and (Ar[Bu-t]N)(3)MoP with MesCNO is proposed to occur by nucleophilic attack by the lone pair of electrons on the phosphine or phosphide to the electrophilic C atom of MesCNO forming an adduct rather than direct attack at the terminal O. This mechanism is supported by computational studies. In addition, reaction of the N-heterocyclic carbene SIPr (SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene) with MesCNO results in formation of a stable adduct in which the lone pair of the carbene attacks the C atom of MesCNO. The crystal structure of the blue SIPr center dot MesCNO adduct is reported, and resembles one of the computed structures for attack of the lone pair of electrons of Me3P on the C atom of MesCNO. Furthermore, this adduct in which the electrophilic C atom of MesCNO is blocked by coordination to the NHC does not undergo OAT with R3P. However, it does undergo rapid OAT with coordinatively unsaturated metal complexes such as (Ar[Bu-t]N)(3)V since these proceed by attack of the unblocked terminal O site of the SIPr center dot MesCNO adduct rather than at the blocked C site. OAT from MesCNO to pyridine, tetrahydrothiophene, and (Ar[Bu-t]N)(3)MoN was found not to proceed in spite of thermochemical favorability.
• Synthesis, structure, and thermochemistry of adduct formation between N-heterocyclic carbenes and isocyanates or mesitylnitrile oxide
  作者：Manuel Temprado、Subhojit Majumdar、Xiaochen Cai、Burjor Captain、Carl D. Hoff

  DOI：10.1007/s11224-013-0305-2

  日期：2013.12

  Reaction of N-heterocyclic carbenes (NHCs) with isocyanates yields stable zwitterionic imidates/amidates in toluene solution. These compounds were fully characterized and the crystal structures of several species were determined by X-ray crystallography. The thermochemistry of binding of these and related species was studied by solution calorimetry. Comparison is made of the enthalpies of binding of NHC to isocyanates (RNCO) and isomeric nitrile oxides (RCNO) as well as CO2. DFT calculations were performed to additionally assess the nature of bonding in these compounds.

  N-heterocyclic carbenes（NHC）与异氰酸酯反应后，在甲苯溶液中产生了稳定的齐聚亚胺酸盐/酰胺酸盐。对这些化合物进行了全面表征，并通过 X 射线晶体学确定了几种化合物的晶体结构。通过溶液量热法研究了这些化合物和相关化合物的结合热化学。比较了 NHC 与异氰酸酯 (RNCO) 和异构腈氧化物 (RCNO) 以及 CO2 的结合焓。此外，还进行了 DFT 计算，以进一步评估这些化合物的键合性质。