acetylacetonatodicarbonylrhodium(l)

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: acetylacetonatodicarbonylrhodium(l)
• 英文别名: Rh(acac)(CO)2；Rh(CO)2acac；(acetylacetonato)dicarbonylrhodium(I)；[Rh(acetylacetonate)(CO)2]；dicarbonylacetylacetonato rhodium(I)；rhodium(I) dicarbonyl acetylacetonate；dicarbonyl(acetylacetonato)rhodium；rhodium dicarbonyl acetylacetonate；Rh(acetylacetonato)(CO)2；Rh(acetylacetone)(CO)2；dicarbonyl(2,4-pentanedionato)rhodium(I)
• 化学式: C₇H₇O₄Rh
• 分子量: 258.036
• InChiKey: BZCAWKOPWNIDOC-FGSKAQBVSA-M

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：

  acetylacetonatodicarbonylrhodium(l) 在 氢气 作用下， 以 二氧化碳 为溶剂， 生成 铑
  参考文献：
  名称：

  二氧化碳诱导的离子液体中铑纳米粒子的制备及其在选择性加氢中的应用

  摘要：

  在陷阱中：借助超临界CO 2可以生成催化活性的纳米颗粒并将其稳定在固体离子基质中。该方法允许使用不会被归类为离子液体的简单铵盐，并产生固体且易于处理的催化剂材料。这些材料可以选择性地催化高度位阻的芳族烯烃的氢化。

  DOI：

  10.1002/anie.200803773
• 作为产物：
  描述：

  [Rh(μ-Cl)(acetylacetonate)(CO)(COCOC6H5)]2 以 氘代苯 为溶剂， 生成 acetylacetonatodicarbonylrhodium(l)
  参考文献：
  名称：

  Arylglyoxylrhodium Complexes, Their Thermolysis, and Attempted Generation by Carbonylation of an Aroylrhodium Complex

  摘要：

  Reactions of ArCOCOCl (Ar = p-ClC(6)H(4), Ph) with Rh(acac)(CO)(2) proceeded readily to afford dimeric arylglyoxyl rhodium complexes [Rh(mu-Cl)(acac)(CO)(COCOAr)](2). [Rh(mu-Cl)(acac)(CO){COCO(p-ClC(6)H(4))}](2) was characterized by X-ray diffraction. Thermolysis of the products showed that [Rh(mu-Cl)(acac)(CO){COCO(p-ClC(6)H(4))}](2) was more stable than [Rh(mu-Cl)(acac)(CO)(COCOPh)](2). The reaction of p-CH(3)OC(6)H(4)COCOCl with Rh(acac)(CO)(2) did not form a similar dimeric complex as final product, but gave p-CH(3)OC(6)H(4)COCl as major product, showing thermal instability of corresponding arylglyoxyl and aroyl rhodium complexes. The reaction of C(6)F(5)CO-COCl did not form a simlar dimeric complex either, but a mononuclear complex RhCl(acac)(COCOC(6)F(5))(CO)(2) was generated as a transient intermediate, which was readily transformed to a furanone arising from reductive elimination of the acac ligand and C(6)F(5)COCO moiety followed by cyclization. In the thermolysis of [Rh(mu-Cl)(acac)(CO)(COCOAr)](2), only ArCOCl and Rh(acac)(CO)(2) were formed, and any ArCORh species could not be detected during the thermolysis process. However, the reaction of Rh(acac)(CO)(2) with PhCOCl formed RhCl(acac)(CO)(2)(COPh), albeit only to a small extent, suggesting that the reaction is not thermodynamically favored. The reaction of RhCl(CO)(PMe(3))(2) with p-ClC(6)H(4)COCOCl also proceeded cleanly to furnish p-ClC(6)H(4)COCORhCl(2)(CO)(PMe(3))(2). Thermolysis of the complex formed p-ClC(6)H(4)CORhCl(2)(CO)(PMe(3))(2), indicating slow reductive elimination of ClC(6)H(4)COCl as compared with the ArCORh species, generated in the thermolysis of [Rh(mu-Cl)(acac)(CO)(COCOAr)](2). Treatment of ClC(6)H(4)CORhCl(2)(CO)(PMe(3))(2) with carbon monoxide generates p-ClC(6)H(4)COCORhCl(2)(CO)(PMe(3))(2), although the yield was low.

  DOI：

  10.1021/om101079e
• 作为试剂：
  描述：

  烯丙基丙二酸二乙酯 在 acetylacetonatodicarbonylrhodium(l) 、 二甲基苯基硅烷 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 20.0~22.0 ℃ 、101.33 kPa 条件下， 反应 26.0h， 生成 8,8-bis(carbethoxy)-2-(4-methylbenzenesulfonyl)-5-oxo-2,3,5,6a,7,9-hexahydro-1H,6H-azuleno[4,5-c]pyrrole
  参考文献：
  名称：

  铑配合物催化烯二炔的硅引发羰基化碳三环化和[2+2+2+1]环加成反应

  摘要：

  dodec-11-ene-1,6-diynes 或它们的杂原子同系物与由 Rh(acac)(CO)2 催化的氢硅烷在环境温度和 CO 压力下反应得到相应的稠合 5-7-5 三环产物， 5-oxo-1,3a,4,5,7,9-hexahydro-3H-cyclopenta[e]azulenes 或它们的杂原子同系物，通过独特的硅引发的级联羰基化碳三环化 (CO-SiCaT) 工艺以优异的产率获得。还发现5-7-5稠合三环产物可以通过新型的分子内[2+2+2+1]环加成过程由相同类型的烯二炔和CO获得。讨论了这两种三环化过程的特点及其反应机理的根本区别。这种新型的高级环加成反应也已成功应用于 undeca-5 的三环化反应，10-diyn-1-als，提供相应的带有七元内酯部分的 5-7-5 稠环产物。还讨论了烯二炔和二炔底物的相关 [2+2+2] 三环化。这些新发现的反应可以同时构建多个键，在

  DOI：

  10.1021/ja054221m

文献信息

• Steric vs. electronic anomaly observed from iodomethane oxidative addition to tertiary phosphine modified rhodium(i) acetylacetonato complexes following progressive phenyl replacement by cyclohexyl [PR3 = PPh3, PPh2Cy, PPhCy2 and PCy3]
  作者：Alice Brink、Andreas Roodt、Gideon Steyl、Hendrik G. Visser

  DOI：10.1039/b922083f

  日期：——

  electronic parameters of the phosphine ligands as phenyl groups on the tertiary phosphine are progressively replaced by cyclohexyl groups in the series. Second order rate constants for the alkyl formation in the oxidative addition of iodomethane in dichloromethane at 25 °C vary with approximately one order-of-magnitude from 6.98(6) × 10−3 M−1s−1 (PCyPh22) to 55(1) × 10−3 M−1 s−1 (PCy2Ph 3) and do not follow

  乙酰丙酮铑（I）式[Rh（acac）（CO）（PR 3）]的配合物[acac =乙酰丙酮，PR 3 = PPh 3 1，PCyPh 2 2，PCy 2 Ph 3，合成了PCy 3 4 ]，并研究了这些复合物中碘甲烷的氧化加成反应。的光谱和低温（100 K）单晶X射线晶体学数据铑配合物（1-4）表明该化合物的空间和电子参数都有系统的增加。膦叔膦上的苯基等价的配体逐渐被系列中的环己基取代。碘甲烷氧化加成时烷基形成的二阶速率常数。二氯甲烷在25°C时从6.98（6）×10 -3大约以一个数量级变化 M -1秒-1（PCyPh 2 2）至55（1）×10 -3 M -1 s -1（PCy 2 Ph 3），并且没有遵循预期的1到4的电子模式，这表明环己基的柔韧性会显着影响反应性。用于反应的激活参数的范围从35（3）〜44（1）千焦摩尔-1为Δ ħ ≠ 和-140（5）至-154（9）J K -1mol
• Supramolecular bidentate phosphorus ligands based on bis-zinc(ii) and bis-tin(iv) porphyrin building blocks
  作者：Vincent F. Slagt、Piet W. N. M. van Leeuwen、Joost N. H. Reek

  DOI：10.1039/b702462m

  日期：——

  Selective metal–ligand interactions have been used to prepare supramolecular bidentate ligands by mixing monodentate ligands with a suitable template. For these assemblies pyridine phosphorus ligands and a zinc(II) porphyrin dimer were used. In the rhodium-catalysed hydroformylation of 1-octene and styrene improved selectivities have been obtained for some of the assembled bidentate ligand systems. In the palladium catalysed asymmetric allylic alkylation similar effects were observed; the enantioselectivity increased by using a bisporphyrin template. The preparation of supramolecular catalyst systems was also explored using tin–oxygen interactions. Dihydroxotin(IV) porphyrin and carboxylic phosphorus ligands assemble into supramolecular ligands and the phosphorus donor atom coordinates to transition metals. The stronger oxygen–tin bond, compared to pyridine–zinc does not result in a better performance of the catalyst.

  选择性金属–配体相互作用已被用于通过混合单齿配体和合适模板来制备超分子双齿配体。在这些组合中，使用了吡啶膦配体和锌(II)卟啉二聚体。在铑催化的1-辛烯和苯乙烯氢甲酰化反应中，一些组合的双齿配体系统获得了更好的选择性。在钯催化的不对称烯丙基烷基化反应中，也观察到了类似的效果；使用双卟啉模板增加了对映选择性。还探索了利用锡–氧相互作用制备超分子催化剂系统的方法。二羟锡(IV)卟啉和羧酸膦配体组装成超分子配体，膦供体原子与过渡金属配位。与吡啶–锌相比，更强的氧–锡键并未导致催化剂性能的提升。
• Investigation of ligand steric effects on a highly cis-selective Rh(i) cyclopropanation catalyst
  作者：Marianne Lenes Rosenberg、Eirin Langseth、Alexander Krivokapic、Nalinava Sen Gupta、Mats Tilset

  DOI：10.1039/c1nj20343f

  日期：——

  Four new Rh(I) complexes bearing chelating imine-functionalized N-heterocyclic carbene ligands have been synthesized and characterized. The catalytic activity of these new Rh(I) complexes has been tested in the cyclopropanation reaction between ethyl diazoacetate and styrene. One of the new complexes, having ethyl groups on the ligand N-aryl ring, exhibited a reactivity and a cis-diastereoselectivity that were comparable to our previously reported Rh(I) cyclopropanation catalyst of this type, and a higher yield and cis-diastereoselectivity were obtained at lower catalyst loadings and higher temperatures. The other new Rh(I) complexes were found to be inferior to the previously reported Rh(I) cyclopropanation catalyst. The catalytic study gave important information about the effect that changing the steric requirements of the substituents at the ligand system has on the efficiency and cis-diastereoselectivity of the complexes as cyclopropanation catalysts.

  合成了四种新型Rh(I)配合物，它们带有螯合亚胺功能化的N-杂环卡宾配体，并对这些配合物进行了表征。测试了这些新型Rh(I)配合物在二氮乙酸乙酯和苯乙烯的环丙烷化反应中的催化活性。其中一种新型配合物在配体N-芳基环上具有乙基，其反应活性和顺式立体选择性与先前报道的该类型Rh(I)环丙烷化催化剂相当，并在较低催化剂用量和较高温度下获得了更高的产率和顺式立体选择性。其他新型Rh(I)配合物的性能则不如先前报道的Rh(I)环丙烷化催化剂。这项催化研究提供了重要信息，即改变配体系统上取代基的立体要求对配合物作为环丙烷化催化剂的效率和顺式立体选择性的影响。
• Precise Supramolecular Control of Selectivity in the Rh-Catalyzed Hydroformylation of Terminal and Internal Alkenes
  作者：Paweł Dydio、Remko J. Detz、Joost N. H. Reek

  DOI：10.1021/ja4046235

  日期：2013.7.24

  DIM pocket of the ligand results in unprecedented selectivities in hydroformylation of terminal and internal alkenes functionalized with an anionic group. Remarkably, the selectivity controlling anionic group can be even 10 bonds away from the reactive double bond, demonstrating the potential of this supramolecular approach. Control experiments confirm the crucial role of the anion binding for the selectivity

  在这项研究中，我们报告了一系列 DIMPhos 配体 L1-L3，双齿磷配体，配有完整的阴离子结合位点（DIM 口袋）。配位研究表明，这些配体以双齿方式与铑中心结合。在加氢甲酰化条件下的实验证实了单核氢化双羰基铑配合物的形成，这些配合物通常被认为在加氢甲酰化中具有活性。形成的金属配合物仍然与配体结合位点的阴离子物质强结合，而不影响金属配位球。DIMPhos 的这些双功能特性通过铑络合物的晶体结构进一步证明，其中醋酸根阴离子结合在配体的结合位点。催化研究表明，通过结合在配体的 DIM 口袋中进行的底物预组织导致末端和内部烯烃的加氢甲酰化具有前所未有的选择性。值得注意的是，选择性控制阴离子基团甚至可以与反应性双键相距 10 个键，这证明了这种超分子方法的潜力。对照实验证实了阴离子结合对选择性的关键作用。对决定性中间体的 DFT 研究表明，DIM 口袋中的阴离子结合限制了反应双键的旋转自由度。结
• Structure, Electrochemistry and Hydroformylation Catalytic Activity of the Bis(pyrazolylborato)rhodium( <scp>I</scp> ) Complexes [RhBp(CO)P] [P = P(NC ₄ H ₄ ) ₃ , PPh ₃ , PCy ₃ , P(C ₆ H ₄ OMe‐4) ₃ ]
  作者：Anna M. Trzeciak、Beata Borak、Zbigniew Ciunik、Józef J. Ziółkowski、M. Fátima C. Guedes da Silva、Armando J. L. Pombeiro

  DOI：10.1002/ejic.200300517

  日期：2004.4

  improved linear relationship between the oxidation potential and the sum of the ligand EL values for square-planar RhI complexes is also obtained and adjusted values for the Lever SM and IM parameters for the RhI/RhII redox couple are given. The trans influence of phosphanes was not observed in crystals of complexes 2 and 3, in contrast to analogous acetylacetonato complexes in which the Rh−O bonds differ

  式 [RhBp(CO)P] [Bp = 双(吡唑基硼酸盐), P = P(NC4H4)31, PPh32, PCy33, P(C6H4OMe-4)34] 的铑配合物已通过交换乙酰丙酮化物 (acac− ) [Rh(acac)(CO)P] 复合物中的配体。[Rh(acac)(CO)P] 和 [RhBp(CO)P] 配合物的光谱和电化学性质以及 X 射线数据进行了比较，目的是估计两种阴离子配体 (acac) 的相对供体性质。 - 和 Bp-)。循环伏安结果表明，Bp-配体的行为比acac-强得多，Lever EL 配体参数的值与吡唑酯配体的值相同（-0.24 V vs. NHE 每个配位臂）被提出对于双和三（吡唑基）硼酸酯配体，P(C6H4OMe-4)3 也显示出与 P(NC4H4)3 具有相同的 EL 值 (0.69 V)。还获得了氧化电位与方形平面 RhI 复合物的配体 EL 值总和之间的改进线性关系

表征谱图