oxotitanium(IV) meso-tetrakis(4-methylphenyl)porphinato | 65496-72-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: oxotitanium(IV) meso-tetrakis(4-methylphenyl)porphinato
• 英文别名: (5,10,15,20-tetra-p-tolylporphyrinato)titaniumoxo(IV)；(meso-tetra-p-tolylporphyrinato)titanium(IV) oxide；(meso-5,10,15,20-tetra-p-tolylporphyrinato)Ti(O)；(meso-5,10,15,20-tetra-p-tolylporphyrinato)Ti=O；tetra(p-tolyl)porphyrinato titanium (IV) oxide；titanyl meso-tetrakis(4-methylphenyl)porphyrin
• CAS: 65496-72-2
• 化学式: C₄₈H₃₆N₄OTi
• 分子量: 732.72
• InChiKey: WTDQEJJAYOAFKW-HTMHXADGSA-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：

  oxotitanium(IV) meso-tetrakis(4-methylphenyl)porphinato 、 (meso-5,10,15,20-tetra-p-tolylporphyrinato)Ti(η(2)-PhC.tplbond.Ph) 以 甲苯 为溶剂， 以48%的产率得到(μ-oxo)bis[(meso-tetra-p-tolylporphyrinato)titanium(III)]
  参考文献：
  名称：

  Intermetal Oxygen Atom Transfer Reactions of Titanium Porphyrins:  Complete vs Incomplete Atom Transfer. X-ray Structure of (μ-Oxo)bis[(meso-tetra-p-tolylporphyrinato)titanium(III)]

  摘要：

  Treatment of (meso-tetra-p-tolylporphyrinato)titanium(IV) oxide, (TTP)Ti=O, with (octaethylporphyrinato)titanium(III)chloride, (OEP)Ti-Cl, in toluene-d(8) results in the reversible exchange of axial ligands to form (TTP)Ti-Cl and (OEP)Ti=O. The net result is a formal one-electron redox process. This occurs with a second-order rate constant of (2.4 +/- 0.2) x 10(2) M(-1) s(-1) to form an equilibrium mixture with K = 1.7 +/- 0.4 at 20 degrees C (Delta H double dagger = 10.8 +/- 0.4 kcal/mol, Delta S double dagger = -10.7 +/- 1.2 cal/mol . K). Use of pivalate in place of chloride on the Ti(III) complex causes no significant change in the rate of this one-electron redox process. In addition, excess chloride only partially inhibits the rate of oxygen transfer with chlorotitanium(III) complexes. A complete kinetic analysis indicates that these redox processes proceed through two parallel pathways, both involving an inner sphere mu-oxo intermediate. Competing associative and dissociative (chloride or pivalate loss) mechanisms are in effect. Reversible oxo/chloro exchange also occurs between (TTP)TiCl2 and (OEP)Ti=O in CHCl3 to produce (TTP)Ti=O and (OEP)TiCl2 with K = 47 +/- 13 and k(f) = 5 +/- 1 M(-1)s(-1) at 20 degrees C (Delta H double dagger = 11 +/- 1 kcal/mol, Delta S double dagger = 11 +/- 3 cal/mol . K, Delta H degrees = -3.7 +/- 0.8 kcal/mol, and Delta S degrees = -5 +/- 2 cal/mol . K). In contrast, when (TTP)Ti=O is treated with (TPP)Ti(eta(2)-PhC=CPh), incomplete oxygen atom transfer occurs to produce the mu-oxo complex, [(TTP)Ti]O-2. X-ray quality crystals of this complex can be prepared by the slow diffusion of O-2 into a solution of (TTP)Ti(4-picoline)(2). The structure of the mu-oxo complex, C114H90N8OTi2, was determined by single-crystal X-ray diffraction (crystal data: monoclinic, C2/c, a = 32.044(8) Angstrom, b = 16.908(5) Angstrom, c = 18.525(5) Angstrom, beta = 117.91(2)degrees, V = 8869(4) Angstrom(3), Z = 4, R = 5.88%, and R(w) = 15.38%). Key metrical parameters include a Ti-O distance of 1.7941(8) Angstrom, average Ti-N distances of 2.113(3) Angstrom, and a Ti-O-Ti angle of 170.8(2)degrees. The Ti atom is displaced 0.66 Angstrom out of the mean porphyrin plane toward the oxo bridge.

  DOI：

  10.1021/ic960863m
• 作为产物：
  描述：

  (meso-5,10,15,20-tetra-p-tolylporphyrinato)Ti=NPh 在 water 作用下， 以 氘代苯 为溶剂， 生成 oxotitanium(IV) meso-tetrakis(4-methylphenyl)porphinato
  参考文献：
  名称：

  Berreau, Lisa M.; Young Jr., Victor G.; Woo, L. Keith, Inorganic Chemistry, 1995, vol. 34, # 3, p. 527 - 529

  摘要：

  DOI：

文献信息

• Preparation, structure, and electrochemistry of porphyrinato titanium (IV) benzenedithiolates with a trithiole ring, a dithiin ring, and two 2-cyanoethylthio groups
  作者：Takeshi Kimura、Yusuke Muraoka、Kaori Amano、Toshiyuki Fujio、Takao Nishikawa、Tsukasa Nakahodo、Hisashi Fujihara

  DOI：10.1142/s1088424618500037

  日期：2018.1

  text]-tolyl)porphyrinato titanium (IV) trithiolobenzenedithiolate (4a), fused with a trithiole ring. Related compounds 4b and 4c were prepared by a similar reaction of 2 with 5,8-diethyl-6,7-dimercaptobenzo[1,4]dithiin (3b) and 3,6-diethyl-4,5-dimercapto-1,2-bis(2-cyanoethylthio)benzene (3c). The structure of 4b was determined by X-ray crystallography. Compound 4c was further treated with cesium hydroxide

  四（[分子式：见正文]-甲苯基）卟啉氧化钛（IV）氧化物（2）与4,7-二乙基-5,6-二巯基苯并[1,2,3]三硫醇（3a）反应生成相应的钛(IV) 配合物，四([分子式：见正文]-甲苯基)卟啉钛 (IV) 三硫代苯二硫醇盐 (4a)，与三硫醇环稠合。相关化合物 4b 和 4c 通过 2 与 5,8-diethyl-6,7-dimercaptobenzo[1,4]dithiin (3b) 和 3,6-diethyl-4,5-dimercapto-1,2 的类似反应制备-双(2-氰基乙硫基)苯(3c)。4b的结构由X射线晶体学确定。化合物4c进一步用氢氧化铯处理以产生相应的二硫醇根阴离子4c2S，其沉积在金电极上。金电极的电化学性质采用循环伏安法测定。简化模型化合物 4b [公式：见正文] 的结构使用带有 Gaussian 09 程序的 DFT 方法进行了优化。优化后的结构用于计算 NMR
• Synthesis, Characterization, and Reactivity of Group 4 Metalloporphyrin Diolate Complexes
  作者：Guodong Du、L. Keith Woo

  DOI：10.1021/om020790g

  日期：2003.2.1

  A number of group 4 metalloporphyrin diolate complexes were synthesized via various approaches. For example, treatment of imido complex (TTP)HfNAriPr with diols resulted in formation of the corresponding diolato complexes (TTP)Hf[OCR1R2CR1R2O] (R1 = R2 = Me, 1; R1 = Me, R2 = Ph, 2; R1 = R2 = Ph, 3). Treatment of (TTP)TiNiPr with diols generated (TTP)Ti[OCR1R2CR1R2O] (R1 = R2 = Me, 5; R1 = Me, R2 =

  通过各种方法合成了许多第4族金属卟啉二醇酸酯复合物。例如，用二醇处理亚胺基络合物（TTP）Hf NAr iPr导致形成相应的二醇基络合物（TTP）Hf [OCR 1 R 2 CR 1 R 2 O]（R 1 = R 2 = Me，1 ; R 1 = Me，R 2 = Ph，2； R 1 = R 2 = Ph，3）。用生成的二醇（TTP）Ti [OCR 1 R 2 CR 1处理（TTP）Ti N i PrR 2 O]（R 1＝ R 2＝ Me，5； R 1＝ Me，R 2＝ Ph，6； R 1＝ H，R 2＝ Ph，7； R 1＝ H，R 2＝对甲苯基，8）。或者，通过（TTP）MCl 2（M = Hf，Ti）与松果酸二钠的复分解反应制备pin酸钛和pin酸钛1和5。complex配合物的取代化学与二醇基配体的碱性密切相关。配合1 - 6进行氧化裂解反应，生成羰基化合物和金属氧卟啉。对于较少取
• Synthesis and Reactivity of Hydrazido(2-) and Imido Derivatives of Titanium(IV) Tetratolylporphyrin
  作者：Joseph L. Thorman、L. Keith Woo

  DOI：10.1021/ic990991l

  日期：2000.3.1

  Titanium porphyrin hydrazido complexes (TTP)Ti = NNR2 (TTP = meso-tetra-p-tolylporphyrinato dianion; R = Me (1), Ph (2)) were synthesized by treatment of (TTP)TiCl2 with 1,1-disubstituted hydrazines H2NNR2 (R = Me, Ph) in the presence of piperdine. The nucleophilic character of the hydrazido moiety was demonstrated in the reactions of complexes 1 and 2 with p-chlorobenzaldehyde, which yielded the titanium

  钛卟啉肼基络合物（TTP）Ti = NNR2（TTP =中-四-对-甲苯基卟啉二阴离子; R = Me（1），Ph（2））是通过用1,1-二取代肼处理（TTP）TiCl2合成的在哌啶存在下，H2NNR2（R = Me，Ph）。在配合物1和2与对氯苯甲醛的反应中证实了肼基部分的亲核特性，这产生了钛氧代配合物（TTP）-Ti ＝ O和相应的。配合物1和2用苯酚或水的质子化分别生成1,1,2-取代的肼和（TTP）Ti（OPh）2或（TTP）Ti =O。观察到对氯苯甲醛和苯酚与（TTP）Ti = NiPr，3具有相似的反应性。配合物3与亚硝基苯的反应干净地形成了偶氮化合物iPrN = NPh和末端氧代产物（TTP）Ti = O.
• Atom Transfer Reactions of (TTP)Ti(η²-3-hexyne): Synthesis and Molecular Structure of <i>trans</i>-(TTP)Ti[OP(Oct)₃]₂
  作者：Joseph L. Thorman、Victor G. Young,、Peter D. W. Boyd、Ilia A. Guzei、L. Keith Woo

  DOI：10.1021/ic0003426

  日期：2001.1.1

  complex, (TTP)Ti(PEt3)2, 6. Although (TTP)Ti(eta 2-3-hexyne) readily abstracts oxygen from epoxides and sulfoxides, the reaction between 1 and O=P(Oct)3 did not result in oxygen atom transfer. Instead, the paramagnetic titanium(II) derivative (TTP)Ti[O=P(Oct)3]2, 7, was formed. The molecular structure of complex 7 was determined by single-crystal X-ray diffraction: Ti-O distance 2.080(2) A and Ti-O-P

  发现杂原子和（TTP）Ti（eta 2-3-hexyne），1（TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dion）之间发生原子和基团转移反应。在用iPrN = C = NiPr，iPrNCO或tBuNCO处理复合物1时，生成了亚氨基衍生物（TTP）Ti = NR（R = iPr，2; tBu，3）。配合物1与CS2，tBuNCS或tBuNCSe之间的反应提供了硫属化合物，（TTP）Ti = Ch（Ch = Se，4; S，5）。用2当量的PEt3处理复合物1产生双（膦）络合物（TTP）Ti（PEt3）2，6。尽管（TTP）Ti（eta 2-3-hexyne）易于从环氧化物和亚砜中提取氧气，但是1和O = P（Oct）3之间的反应没有导致氧原子转移。相反，形成顺磁性钛（II）衍生物（TTP）Ti [O ＝ P（Oct）3] 2，7。配合
• Metalloporphyrin Complex‐Based Nanosonosensitizers for Deep‐Tissue Tumor Theranostics by Noninvasive Sonodynamic Therapy
  作者：Aiqing Ma、Huaqing Chen、Yanhong Cui、Zhenyu Luo、Ruijing Liang、Zhihao Wu、Ze Chen、Ting Yin、Jun Ni、Mingbin Zheng、Lintao Cai

  DOI：10.1002/smll.201804028

  日期：2019.2

  effective for deep‐tissue photoacoustic/magnetic resonance dual‐modal imaging to trace the accumulation of nanoparticles in tumors. Moreover, MnTTP‐HSA intriguingly achieves high SDT efficiency for simultaneously suppressing the growth of bilateral tumors away from ultrasound source in mice. This work develops a deep‐tissue imaging‐guided SDT strategy through well‐defined metalloporphyrin nanocomplexes

  金属配合物被广泛用作抗癌药物，而传统化学疗法的严重副作用需要新的治疗方法。声动力疗法（SDT）通过激活声敏剂和引发活性氧（ROS）损伤恶性组织，提供了一种显着的非侵入性超声（US）治疗方法。在这项工作中，合成了三种金属4-甲基苯基卟啉（TTP）复合物（MnTTP，ZnTTP和TiOTTP），并与人血清白蛋白（HSA）封装在一起以形成新型的纳米声增敏剂。这些纳米声增敏剂会产生大量的单线态氧（1 O 2）在美国辐射下，重要的是在深部组织深达11厘米的情况下表现出出色的美国可激活能力。与ZnTTP-HSA和TiOTTP-HSA相比，MnTTP-HSA表现出最强的ROS活化行为，这是由于密度函数理论所占的最低最高分子轨道-最低的未占用分子轨道间隙能。对于深组织光声/磁共振双峰成像，以追踪纳米颗粒在肿瘤中的积累，它也很有效。此外，MnTTP-HSA有趣地实现了高SDT效率，同时抑制了小鼠远离超声源的