(2,3,7,8,12,13,17,18-octaethylporphyrinato)rhodium(III) chloride | 36670-30-1

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：

(2,3,7,8,12,13,17,18-octaethylporphyrinato)rhodium(III) chloride 在 sodium hydroxide 、 sodium tetrahydroborate 作用下，以乙醇为溶剂，生成 (OEP)Rh(1-)

参考文献：

名称：

环丙烷衍生物与八乙基卟啉精鎓（I）阴离子的开环裂解反应

摘要：

一价八乙基卟啉原鎓（I）阴离子（I）显示出非常强的亲核特性。I的亲核攻击影响了杂环丙烷，被吸电子基团取代的环丙烷以及高应变分子（如四环烷和双环丁烷）的开环裂解。生成的有机ho（III）卟啉的PMR光谱表明，构型反转发生在反应中心。

DOI：

10.1016/s0022-328x(00)94405-x
作为产物：

描述：

octaethylporphyrinatorhodium(II) dimer 以二氯甲烷-D2 为溶剂，以0%的产率得到(2,3,7,8,12,13,17,18-octaethylporphyrinato)rhodium(III) chloride

参考文献：

名称：

Generation of an (alkoxycarbonyl)rhodium complex in an alcohol analog of the water-gas shift reaction

摘要：

(Octaethylporphyrinato)rhodium(II) dimer ((OEPRh)2, 1) reacts with CO and ethanol in CH2Cl2 to give (octaethylporphyrinato)rhodium(III) chloride (5), (ethoxycarbonyl)(octaethylporphyrinato) rhodium(III) (OEPRh(CO)OEt, 6), and formyl(octaethylporphyrinato)rhodium-(III) (2). The structure of 6 was clarified by X-ray diffraction analysis. Complex 6 crystallized in the monoclinic space group P2(1)/n (No. 14) with a = 14.581 (1) angstrom, b = 14.181 (2) angstrom, c = 17.4530 (9) angstrom, V = 3608.8 (9) angstrom3, Z = 4, R = 0.046, R(w) = 0.051, and T = 293 K for 415 parameters and 4864 reflections. The H-1 and C-13 spectral properties of 2 and 6 in CD2Cl2 were determined and the behaviors of 1, 2, (octaethylporphyrinato)rhodium(III) hydride (3), and 6 in CH2Cl2 solvent were examined. Photolysis of 2 in CH2Cl2 at 300 nm afforded (octaethylporphyrinato)rhodium-(III) chloride. Treatment of OEPCoNa with acetic anhydride in ethylene glycol dimethyl ether afforded acetyl(octaethylporphyrinato)cobalt(III) and an analogous experiment with acetic formic anhydride generated an acyl(octaethylporphyrinato)cobalt(III) complex.

DOI：

10.1021/om00028a033
作为试剂：

描述：

3-庚炔在 sodium tetrahydroborate 、 (2,3,7,8,12,13,17,18-octaethylporphyrinato)rhodium(III) chloride 、氧气作用下，以四氢呋喃为溶剂，反应 50.0h，生成 3-庚醇、 4-庚醇

参考文献：

名称：

Catalytic reactions of metalloporphyrins. 3. Catalytic modification of hydroboration-oxidation of olefins with rhodium(III) porphyrin as catalyst

摘要：

DOI：

10.1021/jo00388a037

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文献信息

Catalytic reactions of metalloporphyrins.

作者：Y. Oayama、Y. Tanaka、Y. Yoshida、H. Toi、H. Ogoshi

DOI：10.1016/s0022-328x(00)99798-5

日期：1987.8

(OEP)RhIII(ClO4) to promote enolization of simple ketones by activation with charge-separated [(OEP)RhIII+ (a Lewis acid) under mild and neutral conditions. The second-order rate constant of (OEP)RhIII(ClO4)-assisted enolization of acetone at 30°C (k2 = 2.6 × 10−4 M−1 sec−1) is 107 times as large as that of its spontaneous enolization in water, where water is both acid and bse.

丙酮和甲基乙基酮在温和的条件下，通过阳离子（八乙基卟啉酮）铑（III）与非配位高氯酸根抗衡阴离子（OEP）Rh III（ClO 4）的配合，在甲基上容易且直接地金属化。乙酰丙酮和乙酰乙酸乙酯在内部亚甲基上类似地金属化。相对于铑配合物和酮而言，丙酮的金属化是顺序的，并且涉及酮的（OEP）Rh III（ClO 4）辅助的速率确定的烯化作用。所得的2-氧丙基丙基铑衍生物容易被亲电子试剂如H +和Br 2裂解，形成CRh键。另一方面，当使用环己酮作为底物时，（OEP）Rh III（ClO 4）有效催化酮的醛醇缩合，其中中间体环己酮烯醇化物与存在的酮或其他羰基化合物反应并再生Rh III配合物。本反应的一个重要方面是（OEP）Rh III（ClO 4）在温和和中性条件下通过与电荷分离的[（OEP）Rh III +（路易斯酸）活化）促进简单酮烯醇化的显着能力。。（OEP）Rh III（ClO 4）辅
Electrocatalytic oxidation of alcohols by a carbon-supported Rh porphyrin

作者：Shin-ichi Yamazaki、Masaru Yao、Naoko Fujiwara、Zyun Siroma、Kazuaki Yasuda、Tsutomu Ioroi

DOI：10.1039/c2cc30888f

日期：——

A Rh porphyrin on carbon black was shown to catalyze the electro-oxidation of several aliphatic alcohols (ethanol, 1-propanol, and 2-propanol) and benzyl alcohols. The overpotentials for alcohol oxidation were very low. The reaction mechanism and substrate specificity are discussed.

研究表明，碳黑上的卟啉能催化几种脂肪醇（乙醇、1-丙醇和 2-丙醇）和苯甲醇的电氧化反应。醇氧化的过电位非常低。对反应机理和底物特异性进行了讨论。
Synthesis of rhodium porphyrin aryls via intermolecular arene carbon-hydrogen bond activation

作者：Xiang Zhou、Qi Li、Thomas C.W. Mak、Kin Shing Chan

DOI：10.1016/s0020-1693(97)05825-8

日期：1998.4

(meta-Cyanophenyl) rhodium porphyrins have been synthesized from the selective activation of a meta carbon-hydrogen bond of PhCN via the reaction of RhCl3 with porphyrins in refluxing PhCN.

（间氰基苯基）铑卟啉是通过RhCl 3与卟啉在回流PhCN中的反应选择性活化PhCN的间碳氢键而合成的。
Reductive Electrochemistry of Rhodium Porphyrins. Disproportionation of Intermediary Oxidation States

作者：Valérie Grass、Doris Lexa、Michel Momenteau、Jean-Michel Savéant

DOI：10.1021/ja964023i

日期：1997.4.1

reduction of rhodium(III) porphyrins in polar aprotic solvents is a two-electron irreversible reaction yielding directly the Rh(I) complex. The cause of this irreversibility is not the metal−metal dimerization of the initially formed Rh(II) complex as believed earlier but rather deligation which generates a secondary Rh(II) species easier to reduce than the starting Rh(III) porphyrin. This is confirmed

在极性非质子溶剂中还原铑 (III) 卟啉是一种双电子不可逆反应，直接生成 Rh(I) 络合物。这种不可逆性的原因不是最初形成的 Rh(II) 络合物的金属 - 金属二聚化，而是产生比起始 Rh(III) 卟啉更容易还原的二级 Rh(II) 物种的去连接。空间位阻的卟啉，例如那些带有禁止两个分子在键合距离处接近的交叉反式篮柄超结构的卟啉，表现出与简单的铑卟啉相同的行为这一事实证实了这一点。这种 ECE-歧化过程的发生，在金属卟啉或类似配合物的氧化还原化学中很少观察到，可能与铑原子移出卟啉平面的趋势有关，特别是在 Rh(I) 氧化态时。值得注意的是，强配体和软配体，例如叔膦，消灭了歧...
1H NMR analysis of porphyrin-stoppered rotaxanes: effect of the porphyrin substituents on the macrocycleElectronic supplementary information (ESI) available: chemical shift data. See http://www.rsc.org/suppdata/nj/b4/b403707c/

作者：Taichi Ikeda、Masumi Asakawa、Toshimi Shimizu

DOI：10.1039/b403707c

日期：——

shorter) and three porphyrin rhodium chlorides having different substituents. The chemical shift changes in 1H NMR spectra, due to the anisotropic shielding effects by the aromatic rings, enabled us to estimate the molecular structure. In the cases of the rotaxanes with relatively shorter thread, the conformation of the macrocycle proved to be affected by the substituents in the terminal porphyrin. This result

六种卟啉塞住轮烷通过两根线（相对较长和较短）和三种具有不同取代基的卟啉铑氯化物的组合制备氯乙烯。化学位移的变化1 H NMR谱由于芳香环的各向异性屏蔽作用，使我们能够估计分子结构。在这种情况下轮烷相对较短的螺纹，大循环被证明受末端取代基的影响卟啉。此结果表明大循环和终端卟啉。该结果将导致可以调节分子的旋转运动的分子装置的新颖设计。大循环通过终端卟啉或从大循环到终端卟啉。

(2,3,7,8,12,13,17,18-octaethylporphyrinato)rhodium(III) chloride | 36670-30-1

计算性质

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