| 101078-21-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• CAS: 101078-21-1
• 化学式: 9C₁₆H₃₆N*O₆₂P₂V₃W₁₅
• 分子量: 6146.7
• InChiKey: VGJDXBDDMNJQAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.15
• 重原子数：
  34.0
• 可旋转键数：
  12.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  189.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 以 二氯甲烷 为溶剂， 以59%的产率得到
  参考文献：
  名称：

  Synthesis and Spectroscopic Characterization of a Dawson Trivanadium-Substituted Polyoxotungstate-Supported {(Cp^*Rh)₂}⁴⁺Complex; (Buⁿ₄N)₅[(Cp^*Rh)₂P₂W₁₅V₃O₆₂]

  摘要：

  一种新型的基于聚氧钨酸的2:1型Cp*Rh2+复合物（Bun4N）5[(Cp*Rh)2P2W15V3O62]（Cp* = C5Me5）是通过Dawson三钒取代聚氧钨酸（Bun4N）9[α-1,2,3-P2W15V3O62]与等摩尔量的[Cp*RhCl2]2在冰冷的CH2Cl2中的直接反应合成的，无需使用银（I）盐来去除前体的氯离子。

  DOI：

  10.1246/cl.2000.410
• 作为产物：
  描述：

  tetra-n-butylammonium hydroxide 、 (tetrabutylammonium)5[H4P2W15V3O62] 以 水 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Trisubstituted heteropolytungstates as soluble metal oxide analogs. III. Synthesis, characterization, phosphorus-31, silicon-29, vanadium-51, and 1- and 2-D tungsten-183 NMR, deprotonation, and proton mobility studies of organic solvent solute forms of HxSiW9V3O40x-7 and HxP2W15V3O62x-9

  摘要：

  DOI：

  10.1021/ja00271a025

文献信息

• An All-Inorganic, Polyoxometalate-Based Catechol Dioxygenase That Exhibits >100 000 Catalytic Turnovers
  作者：Heiko Weiner、Richard G. Finke

  DOI：10.1021/ja991503b

  日期：1999.10.1

  Following a critical analysis of the dioxygenase literature and injection of the insights therein into the development of new dioxygenase catalysts, two new, of four total exemplary, polyoxoanion precatalysts have been synthesized, characterized, and then discovered to exhibit record catalytic lifetime 3,5-di-tert-butylcatechol (DTBC; 1) dioxygenase activity using molecular oxygen as the terminal oxidant. A total of 24 additional polyoxoanion and other precatalysts have also been surveyed for their DTBC dioxygenase activity. The four exemplary precatalyst complexes are the trivanadium(V)-containing, orange-red parent polyoxoanions (n-Bu4N)(7)[SiW9V3O40], I, and (n-Bu4N)(9)[P2W15V3O62]. IIr and their previously unknown polyoxoanion-supported, dark green iron complexes (n-Bu4N)(5)[(CH3CN)(x)Fe-SiW9V3O40], III, and (n-Bu4N)(5)[(CH3CN)(x)Fe . P2W15V3O62], IV Careful, high (95 +/- 5%) mass balance studies are reported, studies rare in the dioxygenase literature, but studies made possible in the case of I-IV by their high activity and long lifetimes which yielded sizable amounts of isolable, and thus unequivocally characterizable, products (the characterization of products 2, 3, 4, and 6 includes single-crystal X-ray crystallography structures): 3,5-di-tert-butyl-1-oxacyclohepta-3,5-diene-2,7-dione (muconic acid anhydride), 2; 4,6-di-tert-butyl-2H-pyran-2-one, 3; a new, previously unidentified product (once misidentified in the literature), spiro[1,4-benzodioxin-2(3H), 2'-[2H]pyran]-3-one, 4',6,6',8-tetrakis(1,1-dimethylethyl), 4; 3,5-di-tert-butyl-5-(carboxymethyl)-2-furanone, 5; and the autoxidation product, 3,5-di-tert-butyl-1,2-benzoquinone, 6. Quantitative yields for each of the above products are also reported. Solvent effects on the dioxygenase reaction are evaluated by survey studies in 5 solvents; the highest yields are observed in non-coordinating solvents such as 1,2-dichloroethane. Oxygen uptake studies are reported; the results confirm the 1 O-2:1 DTBC stoichiometry which defines a catechol dioxygenase and address, for the first time, the details of how this similar to 1:1 stoichiometry actually arises from the Linear combination of the individual stoichiometries of the five, formally parallel, major reactions yielding the five major products. Initial kinetic studies are also reported; the O-2 uptake kinetics reveal a novel product and catalyst evolution mechanism consisting of an A --> B induction period, followed by an A + B --> 2 B autocatalytic step for complexes I and III, where A = O-2 and B is a product of the DTBC plus O-2 reaction Catalyst lifetime experiments with (n-Bu4N)(5)[(CH3CN)(x)Fe . SiW9V3O40], III, as a prototype precatalyst reveal a DTBC dioxygenase catalytic Lifetime of > 100 000; total catalytic turnovers (TTOs), a record compared re any reported dioxygenase, man-made or enzymic.A Summary and Conclusions section is presented, as is a list of the needed additional, in-progress, kinetic, mechanistic, and catalyst isolation and characterization studies. The long-term goal of such studies is the development of even longer-lived, more selective dioxygenase catalysts able to oxygenate the full range of interesting substrates of enzymic dioxygenases, as well as abiological substrates such as propene.