(5,10,15,20-tetraphenylporphyrinato)cobalt(III)(1+) | 38414-01-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (5,10,15,20-tetraphenylporphyrinato)cobalt(III)(1+)
• 英文别名: cobalt(III) 5,10,15,20-tetraphenylporphine；(tetraphenylporphyrinato)cobalt(III)；cobalt tetraphenylporphyrin cation；cobalt(III) tetraphenylporphyrin；Co(meso-tetraphenylporphyrin)⁺；Co(tetraphenylporphyrin)
• CAS: 38414-01-6
• 化学式: C₄₄H₂₈CoN₄
• 分子量: 671.726
• InChiKey: ZMPKDYPCHTXPCA-DAJBKUBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.56
• 重原子数：
  49.0
• 可旋转键数：
  4.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  34.58
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (5,10,15,20-tetraphenylporphyrinato)cobalt(III)(1+) 在 1,1,2,2-tetrachloroethane or CCl₄ 作用下， 以 二氯甲烷 为溶剂， 生成 {(TPP)Co}(2+)
  参考文献：
  名称：

  Gasyna, Zbigniew; Browett, William R.; Stillman, Martin J., Inorganic Chemistry, 1984, vol. 23, # 3, p. 382 - 384

  摘要：

  DOI：
• 作为产物：
  描述：

  cobalt(II) 5,10,15,20-tetraphenylporphyrin 在 O₂ 、 Sc(CF₃SO₃)3 、 C₄N₂(C₅H₄N)4 作用下， 以 乙腈 为溶剂， 生成 (5,10,15,20-tetraphenylporphyrinato)cobalt(III)(1+)
  参考文献：
  名称：

  荧光和电子转移的 OFF-OFF-ON 切换取决于主配体与客体金属离子的逐步复杂形成

  摘要：

  在 2,3,5,6-四(2-吡啶基)吡嗪 (TPPZ) 和一系列金属离子 (M(n+) = Sc3+, Y3+, Ho3+, Eu3+, Lu3+, Nd3+, Zn2+, Mg2+, Ca2+, Ba2+, Sr2+, Li+)，其中 TPPZ 形成 2:1 复合物 [(TPPZ)2-M(n+)] 和 1:1 复合物 [TPPZ-M(n+)]，Mn+ 在低和高分别为金属离子浓度。当 2:1 (TPPZ)2-M(n+) 复合物转化为荧光 1:1 TPPZ-M(n+) 复合物时，TPPZ 的荧光强度在高浓度金属离子下开始增加。这被视为金属离子的“OFF-OFF-ON”荧光传感器，取决于 TPPZ 和金属离子之间的逐步复合物形成。TPPZ-M(n+) 配合物的荧光量子产率因金属价态而异，其中二价金属配合物（TPPZ-M2+）的荧光量子产率远大于三价金属配合物（TPPZ-M3+）的荧光量子产率。另一方面，(TPPZ)2-M(n+)

  DOI：

  10.1021/ja0748480
• 作为试剂：
  描述：

  六甲基苯 在 (5,10,15,20-tetraphenylporphyrinato)cobalt(III)(1+) 、 氧气 作用下， 以 乙腈 为溶剂， 生成 hexamethylbenzene cation radical
  参考文献：
  名称：

  使用水作为氧源和双氧作为氧化剂的钴卟啉配合物的光催化氧化反应

  摘要：

  在含有钴卟啉复合物 CoII(TPP)（TPP2- = 四苯基卟啉二价阴离子）、水和三氟甲磺酸 (HOTf) 的 O2 饱和乙腈溶液的可见光照射下，六甲苯发生光催化氧化，通过单光子-二-电子过程，得到五甲基苯甲醇和过氧化氢作为产物，周转数>6000；在该反应中，H2O 和 O2 分别用作氧源和双电子氧化剂。通过电子顺磁共振、时间分辨荧光和瞬态吸收测量以及用 H218O 和 18O2 进行的 18O 标记实验阐明了光催化机制。据我们所知，

  DOI：

  10.1021/jacs.9b02864

文献信息

• Scandium Ion-Promoted Reduction of Heterocyclic NN Double Bond. Hydride Transfer vs Electron Transfer
  作者：Shunichi Fukuzumi、Junpei Yuasa、Tomoyoshi Suenobu

  DOI：10.1021/ja026592y

  日期：2002.10.1

  [Sc(3+)] for the Sc(3+)-promoted hydride transfer, which proceeds via Sc(3+)-promoted electron transfer from AcrH(2) to Ph(2)Tz, followed by proton transfer from AcrH(2)(*)(+) to the 1:1 Ph(2)Tz(*)(-)-Sc(3+) complex and the subsequent facile electron transfer from AcrH(*) to Ph(2)TzH(*). The effects of counteranions on the Sc(3+)-promoted electron transfer and hydride transfer reactions are also reported

  氢化物从 10-甲基-9,10-二氢吖啶 (AcrH(2)) 转移到 3,6-二苯基-1,2,4,5-四嗪 (Ph(2)Tz)，其中包含一个 N=N 双键, 在 Sc(OTf)(3) (OTf = OSO(2)CF(3)) 存在于 298 K 的脱气乙腈 (MeCN) 中时有效发生，而在没有 Sc(3+) 的情况下不发生反应。观察到的二阶速率常数 (k(obs)) 随 Sc(3+) 浓度的增加而增加，以接近有限的值。当 AcrH(2) 被双氘化化合物 (AcrD(2)) 取代时，Sc(3+) 促进的氢化物转移的速率表现出相同的主要动力学同位素效应 (k(H)/k(D) = 5.2+ /-0.2)，与 Sc(3+) 浓度无关。钪离子还促进了从 CoTPP（TPP(2)(-) = 四苯基卟啉二价阴离子）和 10,10'-二甲基-9,9'-联吖啶 [(AcrH)(2)] 到 Ph(2)Tz 的电子转移，而在没有
• Scandium Ion-Promoted Photoinduced Electron-Transfer Oxidation of Fullerenes and Derivatives by <i>p</i>-Chloranil and <i>p</i>-Benzoquinone
  作者：Shunichi Fukuzumi、Hisahiro Mori、Hiroshi Imahori、Tomoyoshi Suenobu、Yasuyuki Araki、Osamu Ito、Karl M. Kadish

  DOI：10.1021/ja016335d

  日期：2001.12.19

  3C(60) to p-benzoquinone increases with an increase in Sc(3+) concentration ([Sc(3+)]) to exhibit a first-order dependence on [Sc(3+)], changing to a second-order dependence at the high concentrations. Such a mixture of first-order and second-order dependence on [Sc(3+)] is also observed for a Sc(3+)-promoted electron transfer from CoTPP (TPP(2-) = tetraphenylporphyrin dianion) to p-benzoquinone. This

  在三氟甲磺酸钪的存在下，发生从 C(60) 的三重激发态到对氯苯醌的有效光诱导电子转移，产生 C(60) 自由基阳离子，其在 980 nm 处具有诊断性 NIR（近红外）吸收带，而在苯甲腈中不存在钪离子的情况下，不会发生从 C(60) (3C(60)) 的三重激发态到对氯苯醌的光致电子转移。电子转移速率服从准一级动力学，准一级速率常数随着对氯苯醌浓度的增加而线性增加。观察到的电子转移 (k(et)) 的二阶速率常数随着钪离子浓度的增加而线性增加。与 C(60)/p-氯醌/Sc(3+) 系统的情况相比，从 3C(60) 到对苯醌的电子转移的 k(et) 值随着 Sc(3+) 浓度 ([Sc(3+)]) 的增加而增加，以表现出对 [Sc(3) +)]，在高浓度下变为二阶依赖性。对于从 CoTPP（TPP(2-) = 四苯基卟啉二价阴离子）到对苯醌的 Sc(3+) 促进的电子转移，也观察到了对 [Sc(3+)]
• Metal Ion-Catalyzed Cycloaddition vs Hydride Transfer Reactions of NADH Analogues with <i>p</i>-Benzoquinones
  作者：Shunichi Fukuzumi、Yoshinori Fujii、Tomoyoshi Suenobu

  DOI：10.1021/ja016370k

  日期：2001.10.1

  1-Benzyl-4-tert-butyl-1,4-dihydronicotinamide (t-BuBNAH) reacts efficiently with p-benzoquinone (Q) to yield a [2+3] cycloadduct. (1) in the presence of Sc(OTf)(3) (OTf = OSO2CF3) in deaerated acetonitrile (MeCN) at room temperature, while no reaction occurs in the absence of Sc3+. The crystal structure of 1 has been determined by the X-ray crystal analysis. When t-BuBNAH is replaced by 1-benzyl-1,4-dihydronicotinarnide (BNAH), the Sc3+-catalyzed cycloaddition reaction of BNAH with Q also occurs to yield the [2+3] cycloadduct. Sc3+ forms 1:4 complexes with t-BuBNAH and BNAH in MeCN, whereas there is no interaction between Sc3+ and Q. The observed second-order rate constant (k(obs)) shows a first-order dependence on [Sc3+] at low concentrations and a second-order dependence at higher concentrations. The first-order and the second-order dependence of the rate constant (k(et)) on [Sc3+] was also observed for the Sc3+-promoted electron transfer from CoTPP (TPP = tetraphenylporphyrin dianion) to Q. Such dependence of k(et) on [Sc3+] is ascribed to formation of 1:1 and 1:2 complexes between Q(.-) and Sc3+ at the low and high concentrations of Sc3+ respectively, which results in acceleration of the rate of electron transfer. The formation constants for the 1:2 complex (K-2) between the radical anions of a series of p-benzoquinone derivatives (X-Q(.-)) and Sc3+ are determined from the dependence of k(et) on [Sc3+]. The K-2 values agree well with those determined from the dependence of k(obs) on [Sc3+] for the Sc3+-catalyzed addition reaction of t-BuBNAH and BNAH with X-Q. Such an agreement together with the absence of the deuterium kinetic isotope effects indicates that the addition proceeds via the Sc3+-promoted electron transfer from t-BuBNAH and BNAH to Q. When Sc(OTf)(3) is replaced by weaker Lewis acids such as Lu(OTf)(3), Y(OTf)(3), and Mg(ClO4)(2), the hydride transfer reaction from BNAH to Q also occurs besides the cycloaddition reaction and the k(obs) value decreases with decreasing the Lewis acidity of the metal ion. Such a change in the type of reaction from a cycloaddition to a hydride transfer depending on the Lewis acidity of metal ions employed as a catalyst is well accommodated by the common reaction mechanism featuring the metal-ion promoted electron transfer from BNAH to Q.
• Fukuzumi, Shunichi; Mochizuki, Seiji; Tanaka, Toshio, Inorganic Chemistry, 1989, vol. 28, # 12, p. 2459 - 2465
  作者：Fukuzumi, Shunichi、Mochizuki, Seiji、Tanaka, Toshio

  DOI：——

  日期：——
• One-electron oxidation of chlorophyll a and (tetraphenylporphyrinato)cobalt(II) by various metalloporphyrin cation radicals. Kinetic spectrophotometric studies
  作者：P. Neta、Varda Grebel、Haim Levanon

  DOI：10.1021/j150614a032

  日期：1981.7