(nitrosyl)(meso-tetraphenylporphyrinato)iron(II) | 52674-29-0

• 英文名称: (nitrosyl)(meso-tetraphenylporphyrinato)iron(II)
• 英文别名: [Fe(TPP)(NO)]
• CAS: 52674-29-0
• 化学式: C₄₄H₂₈FeN₅O
• 分子量: 698.586
• InChiKey: SIBQGNIOJPDCCG-YKKPBKTHSA-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：

  (nitrosyl)(meso-tetraphenylporphyrinato)iron(II) 在 tetrabutylammonium borohydride 作用下， 以 二氯甲烷 为溶剂， 生成 Fe(tetraphenylporphyrin)NO(1-)
  参考文献：
  名称：

  Ryan, Michael D.; Feng, DiWei; Choi, In-Kyu, Recueil des Travaux Chimiques des Pays-Bas, 1987, vol. 106, p. 325 - 325

  摘要：

  DOI：
• 作为产物：
  描述：

  (η(2)-N-phenyl-N-nitrosohydroxylaminato)(meso-tetraphenylporphyrinato)iron(III) * 0.1 CH2Cl2 在 triflic acid 作用下， 以 二氯甲烷 为溶剂， 以34-40的产率得到(nitrosyl)(meso-tetraphenylporphyrinato)iron(II)
  参考文献：
  名称：

  Metalloporphyrins with X[N2O2]- Ligands. Novel High-Spin (N-Phenyl-N-nitrosohydroxylaminato)(meso-tetraarylporphyrinato)iron(III)

  摘要：

  The first metalloporphyrin complexes containing the biologically important X[N2O2](-) functional group have been synthesized. The X-ray structure of (T(p-OCH3)PP)Fe(ON(Ph)NO) reveals that the cupferron ligand is bound to the central Fe atom through both oxygens, resulting in a large Fe displacement of 0.69 Angstrom from the 24-atom mean porphyrin plane.

  DOI：

  10.1021/ic00127a002
• 作为试剂：
  描述：

  氧化亚氮 在 (nitrosyl)(meso-tetraphenylporphyrinato)iron(II) 三苯基膦 作用下， 以 not given 为溶剂， 生成 一氧化二氮
  参考文献：
  名称：

  O Atom Transfer from Nitric Oxide Catalyzed by Fe(TPP)

  摘要：

  The reaction of NO-Fe(TPP) with low pressures of NO gas proceeds through three distinct transformations, the first of which we suggest is the formation of an N-N-coupled, (NO)(2) adduct intermediate. The subsequent formation of NO(NO2)Fe(TPP), which under these conditions readily loses NO, suggests that it is formed by addition of free NO2 to the starting nitrosyl, A mechanism is proposed which implies that the addition of a competitive O atom acceptor would lead to catalytic production of N2O. In agreement with the proposed mechanism, the formation of N2O is decoupled from the formation of the nitrite by using PPh3 as the competitive acceptor. The mechanism of O atom transfer was examined by cross-labeling experiments, which show that both O atoms in the intermediate are equivalent, even under catalytic conditions. The formation of an intermediate was confirmed by IR spectroscopy of the heterogeneous reaction of an NO:Fe(TPP) film with gaseous NO, in which transient, isotope-sensitive nu (NO) bands are seen prior to NO(NO2)Fe(TPP) formation. Mixed N-14/N-15 label experiments demonstrate coupling between the two bound nitrosyls in the transient species.

  DOI：

  10.1021/ja993643r

文献信息

• Five- and Six-Coordinate Adducts of Nitrosamines with Ferric Porphyrins: Structural Models for the Type II Interactions of Nitrosamines with Ferric Cytochrome P450
  作者：Nan Xu、Lauren E. Goodrich、Nicolai Lehnert、Douglas R. Powell、George B. Richter-Addo

  DOI：10.1021/ic901751z

  日期：2010.5.17

  adducts of synthetic iron porphyrins. The reactions of the cations [(por)Fe(THF)2]ClO4 (por = TPP, TTP, OEP) with dialkylnitrosamines (R2NNO; R2 = Me2, Et2, (cyclo-CH2)4, (cyclo-CH2)5, (PhCH2)2) in toluene generate the six-coordinate high-spin (S = 5/2) [(por)Fe(ONNR2)2]ClO4 compounds and a five-coordinate intermediate-spin (S = 3/2) [(OEP)Fe(ONNMe2)]ClO4 derivative in 57−72% yields (TPP = 5,10,15,20-te

  亚硝胺以其毒性和致癌特性而闻名。亚硝胺的代谢活化通过与含血红素的细胞色素 P450 酶的相互作用发生。我们报告了合成铁卟啉的许多亚硝胺加合物的制备和结构表征。阳离子 [(por)Fe(THF) 2 ]ClO 4 (por = TPP, TTP, OEP) 与二烷基亚硝胺(R 2 NNO; R 2 = Me 2 , Et 2 , ( cyclo -CH 2 ) 4 的反应， (环-CH 2 ) 5 , (PhCH 2 ) 2) 在甲苯中生成六配位高自旋 ( S = 5/2) [(por)Fe(ONNR 2 ) 2 ]ClO 4化合物和五配位中间自旋 ( S = 3/2) [(OEP )Fe(ONNMe 2 )]ClO 4衍生物的产率为 57-72%（TPP = 5,10,15,20-四苯基卟啉二价阴离子，TTP = 5,10,15,20-四-对甲苯基卟啉二价阴离子，OEP = 2 ,3,7,8
• Photoluminescent Properties of Cadmium Selenide in Contact with Solutions and Films of Metalloporphyrins:  Nitric Oxide Sensing and Evidence for the Aversion of an Analyte to a Buried Semiconductor−Film Interface
  作者：Albena Ivanisevic、Mark F. Reynolds、Judith N. Burstyn、Arthur B. Ellis

  DOI：10.1021/ja993855o

  日期：2000.4.1

  concentration dependent and can be fit to the Langmuir adsorption isotherm model to yield binding constants of ∼103−104 M-1. The MTPPCl compounds react irreversibly with NO in solution to form nitrosyl adducts, and these compounds reversibly enhance the CdSe PL intensity when adsorbed onto the semiconductor surface, also with binding constants of ∼103−104 M-1. Films of MTPPCl were prepared on CdSe substrates

  通过在氮饱和二氯甲烷溶液中吸附三价金属卟啉 MTPPCl（TPP = 四苯基卟啉；M = Mn、Fe、Co），蚀刻的 n-CdSe 单晶的带边光致发光 (PL) 强度可逆地猝灭。PL 响应依赖于浓度，可以拟合朗缪尔吸附等温线模型以产生约 103-104 M-1 的结合常数。MTPPCl 化合物与溶液中的 NO 不可逆地反应形成亚硝酰基加合物，这些化合物在吸附到半导体表面时可逆地增强 CdSe PL 强度，结合常数也为~103-104 M-1。通过溶剂蒸发在 CdSe 衬底上制备了 MTPPCl 薄膜。这些涂层用作 NO 检测的传感器：虽然裸露的 CdSe 表面对 NO 气体相对于 N2 没有响应，涂层表面可逆地增强 PL 强度（CoTPPCl）或淬灭它（MnTPPCl 和 FeTPPCl），结合常数约为 1 atm-1。与 PL 结果相反...
• Direct Observation of Nitrosylated Heme in Myoglobin and Hemoglobin by Electrospray Ionization Mass Spectrometry
  作者：Rita K. Upmacis、David P. Hajjar、Brian T. Chait、Urooj A. Mirza

  DOI：10.1021/ja964249l

  日期：1997.10.1

  Using electrospray ionization mass spectrometry (ESI-MS), we demonstrate the direct observation of NO attached to the heme moiety in horse heart myoglobin (Mb) and in the α- and β-chains of human hemoglobin (Hb). It was found that a narrow range of ESI-MS conditions conspire to make observation of Fe−NO interactions challenging, and this is presumably the reason why earlier attempts by other research

  使用电喷雾电离质谱 (ESI-MS)，我们证明了对马心脏肌红蛋白 (Mb) 和人血红蛋白 (Hb) 的 α 和 β 链中血红素部分连接的 NO 的直接观察。发现窄范围的 ESI-MS 条件共同使 Fe-NO 相互作用的观察具有挑战性，这可能是其他研究小组早期尝试通过质谱法检测完整 Fe-NO 产物未成功的原因。对于 Mb 和 Hb，观察到的质量变化与血红素蛋白的 NO 修饰一致。在 NO 存在下 Mb 和 Hb 的载脂蛋白部分的 ESI 质谱表明多肽骨架没有 NO 修饰。Mb/NO 和 Hb/NO 溶液的紫外/可见光谱，在 ESI-MS 分析时记录，证明了血红蛋白II-NO的形成。为了检验 ESI-MS 可观察到完整亚硝基化血红素基团的假设，研究了亚硝基化模型金属卟啉。ESI质量...
• Substituent Effects on the Electronic Absorption and MCD Spectra of Five- and Six-Coordinate Nitrosyl(tetraphenylporphyrinato)iron(II) Complexes
  作者：Tetsuhiko Yoshimura

  DOI：10.1246/bcsj.63.3689

  日期：1990.12

  Electronic absorption and MCD spectra of five- and six-coordinate nitrosyl iron(II) complexes of a series of tetrakis(para-substituted phenyl)porphyrins have been investigated in order to elucidate the cis-effect of para-substituents. The MCD spectroscopy was more sensitive to the substituent effect than the electronic absorption spectroscopy.

  已经研究了一系列四（对位取代苯基）卟啉的五和六配位亚硝酰基铁（II）配合物的电子吸收和 MCD 光谱，以阐明对位取代基的顺式效应。MCD 光谱对取代基效应比电子吸收光谱更敏感。
• Synthetic Iron Porphyrins for Probing the Differences in the Electronic Structures of Heme <i>a</i>₃, Heme <i>d</i>, and Heme <i>d</i>₁
  作者：Sk Amanullah、Paramita Saha、Rajat Saha、Abhishek Dey

  DOI：10.1021/acs.inorgchem.8b02063

  日期：2019.1.7

  to their function. Herein, we report the synthesis of a series of iron porphyrinoids, which bear electron-withdrawing groups and/or are saturated at the β-pyrrolic position, mimicking the structural variation of naturally occurring hemes. The effects of the aforementioned factors were systematically studied using a combination of electrochemistry, spectroscopy, and theoretical calculations with the carbon

  各种血红素衍生物本质上是普遍存在的，具有与其功能互补的不同结构。在本文中，我们报道了一系列铁卟啉类化合物的合成，这些类卟啉类化合物具有吸电子基团和/或在β-吡咯位置上饱和，模仿了天然血红素的结构变异。利用电化学，光谱学和理论计算结合这些铁卟啉类化合物的一氧化碳（CO）和一氧化氮（NO）加合物，系统地研究了上述因素的影响。铁卟啉类化合物的还原电位在几百毫伏内变化，加合物的X–O（X = C，N）振动在10–15 cm –1之间变化。密度泛函理论计算表明，吸电子基团的存在和吡咯环的饱和降低了大环的π*受体轨道能，从而削弱了铁与CO和NO的键合。已经提出了关于为什么含有亚硝酸还原酶的细胞色素c和含有亚硝酸还原酶的细胞色素cd 1遵循不同的亚硝酸还原机理的假设。这项研究还有助于合理化选择血红素a 3而不是细胞色素c氧化酶中最丰富的血红素b辅因子。