Cr(II)(meso-tetraphenylporphyrinato) | 58344-06-2

• 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: Cr(II)(meso-tetraphenylporphyrinato)
• 英文别名: chromium (d(3))-tetraphenylporphyrin；Cr(II)(TPP)
• CAS: 58344-06-2
• 化学式: C₄₄H₂₈CrN₄
• 分子量: 664.729
• InChiKey: NOFMEAOHIQIURG-DAJBKUBHSA-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：

  Cr(II)(meso-tetraphenylporphyrinato) 在 氧气 作用下， 以 二氯甲烷 为溶剂， 生成 (meso-tetraphenylporphyrinato)-chloro-pyridyl-chromium
  参考文献：
  名称：

  Dual Application of (Aqua)(Chlorido)(Porphyrinato)Chromium(III) as Hypersensitive Amine-Triggered ON Switch and for Dioxygen Activation

  摘要：

  Although synthesis and substitution reactions of chlorido chromium(III) porphyrins Cr-III(TPP)(Cl)(L) (H2TPP = 5,10,15,20-tetraphenyl porphyrin, L = pyridine, H2O, ROH, etc.), have been well-established in coordination chemistry for decades, an unexpected dichotomous reactivity of Cr-III(TPP)(Cl)(H2O) (1) toward amines is disclosed here. This reactivity leads to the application of 1 as highly sensitive substoichiometric and irreversible ON switch for amine detection by an autocatalytic pathway. The concomitant activation of O-2 by the 1/amine system is furthermore exploited in an electrochemically driven epoxidation of norbonene using O-2 as initial oxidant.

  DOI：

  10.1021/ic501644z
• 作为产物：
  描述：

  nitrido(5,10,15,20-tetraphenylporphyrinato)chromium(V) 在 氧气 作用下， 以 苯 为溶剂， 以0%的产率得到Cr(II)(meso-tetraphenylporphyrinato)
  参考文献：
  名称：

  Pyrolytic reactions of azidochromium(III) porphyrins and azidoiron(III) porphyrins in the solid state

  摘要：

  Azidochromium(III) tetraphenylporphyrin. Cr(III)(tpp)N3 (tpp = 5,10,15,20-tetraphenylporphyrinato), and azidoiron(III) tetraphenylporphyrin, Fe(III)(tpp)N3, in the solid state, were pyrolysed under 10(-5) -10(-6) torr at around 250-degrees-C, liberating nitrogen gas to afford Cr(II)(tpp) and Fe(II)(tpp) as final products, respectively. Cr(v)(tpp)N formed in the process of the Cr(III)(tpp)N3 pyrolysis is reduced to Cr(II)(tpp), although pure Cr(v)(tpp)N prepared independently is not pyrolysed under the same conditions. In the presence of dioxygen in the toluene solutions of these pyrolysed products, Cr(IV)(tpp)O or [Fe(tpp)]2O is formed. The mechanisms of these reactions in the solid state are discussed in comparison with those in solution.

  DOI：

  10.1016/s0277-5387(00)80159-x

文献信息

• The synthesis, reactivity and magnetic susceptibilities of Cr(IV)porphyrin imido complexes, CrN(R), and attempts to form heterobinuclear μ-imido compounds with CrN(R)V and CrN(R)Fe bridges
  作者：Boujemaa Moubaraki、Keith S. Murray、Peter J. Nichols、Scott Thomson、Bruce O. West

  DOI：10.1016/s0277-5387(00)81665-4

  日期：1994.1

  Abstract The reactions of arylazides with chromium(II) porphyrin compounds lead to the production of paramagnetic (d2) imides, CrIV(Por)N(R). The complexes undergo reaction with PPh3, benzaldehyde, CS2, CH3I and styrene leading to transfer of the imido group. Reaction of Cr(Por)N(R) compounds with VIVO(acac)2 and iron(II) salicylaldimines results in the formation of imido-bridged CrIIIN(R)V(V) and

  摘要芳基叠氮化物与铬卟啉化合物的反应导致顺磁性（d2）酰亚胺CrIV（Por）N（R）的产生。配合物与PPh3，苯甲醛，CS2，CH3I和苯乙烯反应，导致亚氨基转移。Cr（Por）N（R）化合物与VIVO（acac）2和铁（II）水杨醛亚胺的反应导致形成亚氨基桥接的CrIIIN（R）V（V）和CrIIIN（R）Fe（III）物种，如磁化率与温度测量值（低至4.3 K）所示。
• The autoxidation of a chromium (<scp>II</scp>) porphyrin: synthesis and structural characterisation by X-ray crystallography of αβγδ-tetraphenyl-porphinato-oxochromium(<scp>IV</scp>)
  作者：John R. Budge、Bryan M. K. Gatehouse、Michael C. Nesbit、Bruce O. West

  DOI：10.1039/c39810000370

  日期：——

  The reaction of dioxygen with αβγδ-tetraphenyl-porphinatochromium (II) in toluene proceeds in two stages; a µ-oxo-chromium(III) intermediate is formed initially and this then further reacts with dioxygen to give the title complex, the structure of which has been determined by X-ray crystallography.

  双氧与αβγδ-四苯基-卟啉铬（II）在甲苯中的反应分两个阶段进行：首先形成一个μ-氧代铬（III）中间体，然后进一步与双氧反应生成标题配合物，该配合物的结构已通过X射线晶体学确定。
• Matrix isolation infrared study of the interaction of dioxygen with chromium(II)tetraphenylporphyrin
  作者：G.G. Martirosyan、G.S. Hovhannisyan、T.S. Kurtikyan、A.V. Iretskii

  DOI：10.1016/j.ica.2021.120439

  日期：2021.9

  The infrared spectra of Cr(II)(TPP) (TPP is meso-tetraphenylporphyrinato dianion) and its adduct with molecular oxygen have been recorded in argon matrices at 10 K, as well as in thin sublimated films. Formation of the Cr(TPP)(O2) adduct have been confirmed using 16O2 and 18O2. The ν(O2) stretching bands are located at 1146 and 1082 cm−1, respectively. These and literature data together with the results

  Cr（II）（TPP）（TPP是内消旋四苯基卟啉二价阴离子）及其与分子氧的加合物的红外光谱已在10 K氩气基质和升华薄膜中记录下来。已经使用16 O 2和18 O 2证实了Cr（TPP）（O 2）加合物的形成。ν（O 2）拉伸带分别位于1146和1082 cm -1处。这些并用我们的DFT计算结果一起文献数据，是与相一致的端部上在分子氧在Cr（III）（TPP）（O装订模式2 -）superoxo复杂。
• Weakening the N–H Bonds of NH₃Ligands: Triple Hydrogen-Atom Abstraction to Form a Chromium(V) Nitride
  作者：Brian J. Cook、Melissa Barona、Samantha I. Johnson、Simone Raugei、R. Morris Bullock

  DOI：10.1021/acs.inorgchem.2c01115

  日期：2022.7.25

  Weakening and cleaving N–H bonds is crucial for improving molecular ammonia (NH3) oxidation catalysts. We report the synthesis and H-atom-abstraction reaction of bis(ammonia)chromium porphyrin complexes Cr(TPP)(NH3)2 and Cr(TMP)(NH3)2 (TPP = 5,10,15,20-tetraphenyl-meso-porphyrin and TMP = 5,10,15,20-tetramesityl-meso-porphyrin) using bulky aryloxyl radicals. The triple H-atom-abstraction reaction results

  弱化和断裂 N-H 键对于改进分子氨 (NH 3 ) 氧化催化剂至关重要。我们报告了双（氨）铬卟啉配合物 Cr(TPP)(NH 3 ) 2和 Cr(TMP)(NH 3 ) 2 (TPP = 5,10,15,20-四苯基)的合成和 H 原子提取反应- meso -porphyrin 和 TMP = 5,10,15,20- tetramesityl- meso - porphyrin) 使用庞大的芳氧基自由基。三重 H 原子提取反应导致 Cr V (por)(≡N) 的形成，氮化物衍生自 NH 3，如 UV-vis 和 IR 以及 Cr(TPP)(≡N) 的单晶结构测定所示。该铬 (V) 氮化物络合物的后续氧化导致形成 Cr III (por)，并断开 Cr≡N 键。计算分析说明了从 Cr II到 Cr V的进展，并评估了从 Cr II -NH 3中提取 H 原子以生成 Cr V ≡N 的能量学。Cr
• 一种金属氮翻转卟啉-羰基钴多功能催化剂在催化环氧化物制备β-内酯中的应用
  申请人：中国科学院大连化学物理研究所

  公开号：CN116041284A

  公开（公告）日：2023-05-02

  本发明公开一种金属氮翻转卟啉‑羰基钴多功能催化剂在催化环氧化物制备β‑内酯中的应用，属于β‑内酯制备技术领域。本发明的催化剂是由路易斯酸金属氮翻转卟啉和羰基钴两部分组成，金属氮翻转卟啉是由氮翻转卟啉与金属形成的内外全配位的特殊金属络合物，金属氮翻转卟啉中的双金属位点协同活化环氧化物的开环过程，提高了环氧化物的活化速率；氮翻转卟啉配体的内核与中心的金属配位时，采用全部去质子化的形式，能够稳定高价态金属阳离子，进而加快羰基化反应决速步中路易斯酸阳离子的释放，使β‑内酯闭环，提高了β‑内酯的选择性。本发明的催化剂催化环氧化物转化为β‑内酯，具有高的活性和选择性，为环氧化物羰基化反应的工业化应用奠定了基础。