[(η(5)-C5Me5)Ir(η(5)-C6H5O)][BF4] | 93612-28-3

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: [(η(5)-C5Me5)Ir(η(5)-C6H5O)][BF4]
• 英文别名: [(η(5)-C5Me5)Ir(η(5)-C6H5O)]BF4；[((CH3)5C5)Ir(η(5)-C6H5O)]BF4；cyclohexa-2,5-dien-1-one;iridium(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;tetrafluoroborate
• CAS: 93612-28-3
• 化学式: BF₄*C₁₆H₂₀IrO
• 分子量: 507.359
• InChiKey: HALFMCBTHVZJJE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(η(5)-C5Me5)Ir(η(5)-C6H5O)][BF4] 在 tetrafluoroboric acid diethyl ether complex 作用下， 以 乙腈 为溶剂， 反应 48.0h， 生成 苯酚
  参考文献：
  名称：

  Selective Aromatic C–H Hydroxylation Enabled by η⁶-Coordination to Iridium(III)

  摘要：

  We report an aromatic C-H hydroxylation protocol in which the arene is activated through eta(6)-coordination to an iridium(III) complex. eta(6)-Coordination of the arene increases its electrophilicity and allows for high positional selectivity of hydroxylation at the site of least electron density. Through investigation of intermediate eta(5)-cyclohexadienyl adducts and arene exchange reactions, we evaluate incorporation of arene pi-activation into a catalytic cycle for C-H functionalization.

  DOI：

  10.1021/acs.organomet.5b00731
• 作为产物：
  描述：

  (ethoxybenzene)(pentamethylcyclopentadienyl)iridium III tetrafluoroborate 以 aq. phosphate buffer 、 重水 为溶剂， 反应 1.0h， 生成 [(η(5)-C5Me5)Ir(η(5)-C6H5O)][BF4]
  参考文献：
  名称：

  铱上的芳烃活化促进芳醚的C–O键裂解

  摘要：

  报道了用于芳基醚的选择性分解的芳烃活化策略。各种芳基的醚类容易通过结合η亲电子五甲基环戊二烯铱中心6 -arene协调，从而产生朝向的Ar-OR键（R =甲基，乙基，PH）的水解和裂解激活复合物。在室温下，在pH 7的磷酸盐水溶液中（或在酸性条件下适度加热），水解迅速发生，释放出醇，同时形成环己二烯基-一的产物。在强酸性条件下，二烯基一的质子化，然后被起始的芳基醚取代，完成了水解循环。机理研究表明，通过亲核攻击的基芳烃的本位位置（键水解步骤进行小号ÑAr机制）。在木质纤维素生物质转化的背景下考虑了观察到的机制。

  DOI：

  10.1021/om5000166

文献信息

• Activation and regioselective ortho-functionalization of phenols promoted by ‘Cp*Ir’ fragment: synthesis, structures and applications to organic synthesis. Cp*=C5Me5
  作者：Jean Le Bras、Hani Amouri、Jacqueline Vaissermann

  DOI：10.1016/s0022-328x(98)00668-8

  日期：1998.9

  recycled in the form [Cp*Ir(μ-I)I]2. Extension of this chemistry to other type of nucleophiles such as phosphines, allows the isolation of a stable iridium η4-phenol tautomer complex [Cp*Ir(η4-exo-2-(PMe3)–C6H5O)]+. The latter was identified by X-ray diffraction and represents the key intermediate for the nucleophilic phenol functionalization reaction and the first molecular structure of a monocyclic phenol

  该类型的若干稳定氧代二烯基的铱配合物的[Cp *的Ir（氧代- η 5 -dienyl）] [BF 4 ]（2B - 6）在高已经准备定量的产率。用NaOMe这些氧代二烯基化合物处理，得到的类型的相应的新颖的中性二烯酮络合物的[Cp *的Ir（氧代η 4 -dienone）]（7 - 11，17）。随后，新的二烯酮-铱配合物被I 2轻度氧化，产生相关的官能化游离酚以及以[Cp * Ir（μ- I）I] 2形式循环的起始有机金属材料。这种化学到其它类型的亲核体如膦的的扩展，允许稳定的隔离铱η 4 -苯酚互变异构体复合物的[Cp *的Ir（η 4 -外-2-（PME 3）-C 6 H ^ 5 O）] +。后者通过X射线衍射鉴定，代表亲核酚官能化反应的关键中间体和单环酚互变异构体配合物的第一个分子结构。最后，介绍并讨论了Cp * Ir系统在有机合成中的用途。
• Double nucleophilic attack on η6-arene(pentamethylcyclopentadienyl)iridium dications. Routes from substituted benzenes to substituted cyclohexenes by addition of two hydrides and two protons
  作者：Stephen L. Grundy、Peter M. Maitlis

  DOI：10.1016/0022-328x(84)80470-2

  日期：1984.9

  preferentially para, and chlorobenzene, ortho. Methoxybenzene was attacked ipso as well as ortho, meta (predominant), and para, and phenol gave only the meta-isomer. p-Xylene gave one isomer and o-xylene and tetralin gave two. Further reduction occurred on reaction with stronger hydride reducers (e.g., sodium bis(methoxyethoxy)dihydroaluminate) to give mixtures of 1- and 2-substituted cyclohexa-1,3-diene complexes

  的配合物[（C 5我5）IR（η 6 -arene）] [BF 4 ] 2（芳烃=甲苯，甲苯d 8，叔丁基苯，甲氧基苯，氯苯，ö二甲苯，p二甲苯，四氢化萘和苯酚）是从芳烃制备并用NaBH降低4到η 5 -cyclohexadienyl络合物。攻击外的芳烃和，但有一个例外，从来没有在取代。甲苯没有表现出网站的偏好，但叔丁基苯被攻击优先对位，和氯苯，邻。甲氧基苯被ipso攻击以及邻位，间位（主要）和对位以及苯酚仅给出间位异构体。对二甲苯得到一种异构体，邻二甲苯和四氢化萘得到两种异构体。与较强的氢化物还原剂（如双（甲氧基乙氧基）二氢铝酸钠）反应，可进一步还原，得到1-和2-取代的环己-1,3-二烯配合物（t-Bu，2-（> 95％）； Me，1-（25％），2-（75％）； Cl，1-（> 95％）； OMe，1-（33％），2-（67％））。所述p二甲苯复杂，得到η的混合物4 -1,4- dimethylcyclohexa-1
• Regioselective Ortho-Functionalization of Phenols Promoted by the “Cp*Ir” Unit in [Cp*Ir(oxo-η⁵-cyclohexadienyl)][BF₄] Complexes
  作者：Jean Le Bras、Hani El Amouri、Jacqueline Vaissermann

  DOI：10.1021/om9606698

  日期：1996.12.24

  A series of alkylated phenols (phenol, 3,5-dimethylphenol and 3,4-dimethylphenol) were complexed by the [Cp*Ir(solvent)(3)][BF4](2) (1) unit prepared in situ; subsequent treatment with NEt(3) produced the (oxo-eta(5)-cyclohexadienyl)iridium complexes [Cp*Ir(eta(5)-C(6)H(3)R(2)O)][BF4] [R = H (2); R = Me (3, 4)]. The X-ray molecular structure of 3 was determined. These (oxo-eta(5)-cyclohexadienyl)iridium derivatives react with NaOMe in methanol to give the novel iridium cyclohexadienone complexes [Cp*Ireta(4)-C(6)H(3)R(2)O(OMe)}] [R = H (5); R = Me (6, 7)] in 75-90% yield with nucleophilic attack occurring exclusively at the ortho-position relative to the C=O function. Addition of HBF4 . Me(2)O to these iridium cyclohexadienone complexes 5-7 affords the starting material (oxo-eta(5)-cyclohexadienyl)iridium derivatives 2-4 with MeOH. Further exposure to HBF4 . Me(2)O produces the corresponding phenolic compounds [Cp*Ir(eta(6)-C(6)H(3)R(2)OH)][BF4](2) (8 - 10); these chemical reactions are accompanied with hapticity changes eta(4) --> eta(5) --> eta(6) of the coordinated pi-hydrocarbon. The novel iridium cyclohexadienone complexes 5-7 can be oxidized easily by iodine to produce the free cyclohexadienones which rearomatize to give the free ortho-substituted phenols 11-13 in yields from 80% to quantitative.
• Le Bras; Amouri; Vaissermann, Inorganic Chemistry, 1998, vol. 37, # 20, p. 5056 - 5060
  作者：Le Bras、Amouri、Vaissermann

  DOI：——

  日期：——
• Ir-Mediated Nucleophilic Ortho-Functionalization of Phenols:  Syntheses, Structures, Scope, and Limitation
  作者：Hani Amouri、Jean Le Bras、Jacqueline Vaissermann

  DOI：10.1021/om980828i

  日期：1998.12.1

  Treatment of [Cp*Ir(eta(5)-PhO)][BF4] (1) with hydride, deuteride, and C-, N-, and S-centered nucleophiles affords the stable eta(4)-phenol tautomers of the type [Cp*Ir(eta(4)-exo-2-(Nu)-C6H5O)] (2-6) Nu = nucleophile}. In all cases regiospecific nucleophilic addition occurs at the ortho-position relative to C=O with exo-stereochemistry. The X-ray molecular structure of the first neutral phenol tautomer [Cp*Ir(eta(4)-exo-2-(CH(COMe)(2))-C6H5O] (4) was determined and provides valuable crystallographic information for an organic phenol tautomer. Oxidation of the novel dienone iridium complexes [Cp*Ir(eta(4)-exo-2-(Nu)-C6H5O)] by iodine provided a different type of products depending dramatically on the nature and electron properties of the 2-exo-nucleophile. For instance R3C-, RO-, and R3P-centered nucleophiles gave the related ortho-functionalized phenols along with the starting material recycled in the form of [Cp*Ir(mu-I)I](2). In dramatic contrast N- and S-centered nucleophiles showed a retronucleophilic addition or C-Nu bond cleavage as demonstrated by complexes 5 and 6 to give the starting material identified spectroscopically and by X-ray structure as [Cp*Ir(eta(5)-PhO)][I] (8). In the latter, a rationale involving a one-electron oxidation process is proposed to explain the experimental results.