十六羰基六铑

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 中文名称: 十六羰基六铑
• 中文别名: 十六羰基合六铑
• 英文名称: hexarhodium hexadecacarbonyl
• 英文别名: [Rh6(CO)16]；carbon monoxide;rhodium
• 化学式: C₁₆O₁₆Rh₆
• 分子量: 1065.6
• InChiKey: SZQABOJVTZVBHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.62
• 重原子数：
  38
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  16
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  十六羰基六铑 以 further solvent(s) 为溶剂， 生成 铑
  参考文献：
  名称：

  Synthesis of Co, Rh and Ir nanoparticles from metal carbonyls in ionic liquids and their use as biphasic liquid–liquid hydrogenation nanocatalysts for cyclohexene

  摘要：

  Stable cobalt, rhodium and iridium nanoparticles are obtained reproducibly by thermal decomposition under argon from Co-2(CO)(8), Rh-6(CO)(16) and Ir-4(CO)(12) dissolved in the ionic liquids BMim(+)BF(4)(-), BMim(+)OTf and BtMA(+)NTf(2)(-) [BMim(+) = n-butyl-methyl-imidazolium, BtMA(+) = n-butyl-tri-methyl-ammonium, OTf = O3SCF3, NTf2- = N-(O2SCF3)(2)]. The very small and uniform nanoparticle size of about 1-3 nm in BMim(+)BF(4)(-) increases with the molecular volume of the ionic liquid anion in BMim(+)OTf and BtMA(+)NTf(2)(-). Characterization of the nanoparticles was done by transmission electron microscopy (TEM), transmission electron diffraction (TED), X-ray powder diffraction (XRPD) and dynamic light scattering (DLS). The rhodium or iridium nanoparticle/IL systems function as highly effective and recyclable catalysts in the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 1900 mol(product)/(mol(metal) h) and quantitative conversion within 1 h at 4 bar H-2 pressure and 75 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.09.050
• 作为产物：
  描述：

  dodecacarbonyltetrarhodium(0) 以 solid 为溶剂， 以>99的产率得到十六羰基六铑
  参考文献：
  名称：

  一系列四核羰基簇Rh 4（CO）12，Rh 2 Co 2（CO）12，RhCo 3（CO）12和Co 4（CO）12的热分解

  摘要：

  已通过程序升温分解研究了氢流中非支撑簇Rh 4（CO）12，Rh 2 Co 2（CO）12，RhCo 3（CO）12和Co 4（CO）12的脱羰作用。给出了热分解的动力学参数，并讨论了团簇的稳定性。从Rh 4（CO）12释放出CO的曲线表明形成了稳定的中间体。在所有四种情况下，甲烷都是逐步形成的，直到大部分CO基团放出为止。

  DOI：

  10.1016/s0022-328x(00)99712-2
• 作为试剂：
  描述：

  1-乙酰哌啶 在 十六羰基六铑 、 氢气 、 molybdenum hexacarbonyl 作用下， 以 乙二醇二甲醚 为溶剂， 160.0 ℃ 、10.0 MPa 条件下， 反应 16.0h， 生成 N-乙基哌啶
  参考文献：
  名称：

  Selective hydrogenation of amides using Rh/Mo catalysts

  摘要：

  Rh/Mo catalysts formed in situ from Rh-6(CO)(16) and MO(CO)(6) are effective for the liquid phase hydrogenation of CyCONH2 to CyCH2NH2 in up to 87% selectivity, without the requirement for ammonia to inhibit secondary amine formation. Use of in situ HP-FTIR spectroscopy has shown that decomposition of metal carbonyl precursors occurs during an extended induction period, with the generation of recyclable, heterogeneous, bimetallic catalysts. Variations in Mo:Rh content have revealed significant synergistic effects on catalysis, with optimum performance at values of ca. 0.6, and substantially reduced selectivities at >= 1. Good amide conversions are noted within the reaction condition regimes 50-100 bar H-2 and 130-160 degrees C. Ex situ characterization of the catalysts, using XRD, XPS and EDX-STEM, has provided evidence for intimately mixed (ca. 2-4 nm) particles that contain metallic Rh and reduced Mo oxides, together with MoO3. Silica-supported Rh/Mo analogues, although active, perform poorly at < 150 degrees C and deactivate during recycle. (c) 2009 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jcat.2009.10.020

文献信息

• Selective Deoxygenation of Various N–O Bonds Catalyzed by Rhodium Carbonyl Clusters in the Presence of H₂O and CO and Their Heterogenization Using Amino-Substituted Polystyrenes
  作者：Kiyotomi Kaneda、Kazuo Fujita、Tetsuya Takemoto、Toshinobu Imanaka

  DOI：10.1246/bcsj.64.602

  日期：1991.2

  amines, and 5) amine oxides to amines. The above-mentioned rhodium catalyst system was heterogenized by using amino-substituted polystyrenes. Rh6 and Rh14 carbonyl clusters of [Rh6(CO)15H]−, [Rh6(CO)15]2−, and [Rh14(CO)25]4−, were formed on the polymer surface. The characteristic features of the catalysis of the polymer-bound rhodium cluster complexes are described in relation to the corresponding homogeneous

  研究了在水煤气变换反应下使用羰基铑化合物对各种 N-O 键的催化脱氧。发现 Rh6(CO)16 和 N,N,N',N'-四甲基-1,3-丙二胺的催化剂体系对以下脱氧反应具有高活性：1) 硝基苯转化为苯胺，2) 脂肪族硝基化合物转化为腈，3) 肟转化为腈，4) 羟胺转化为胺，以及 5) 氧化胺转化为胺。上述铑催化剂体系通过使用氨基取代的聚苯乙烯多相化。[Rh6(CO)15H]-、[Rh6​​(CO)15]2-和[Rh14(CO)25]4-的Rh6和Rh14羰基簇在聚合物表面形成。聚合物结合的铑簇配合物的催化特征与相应的均相配合物有关。
• Identification of Rhodium−Rhenium Nonacarbonyl RhRe(CO)₉. Spectroscopic and Thermodynamic Aspects
  作者：Chuanzhao Li、Liangfeng Guo、Marc Garland

  DOI：10.1021/om0496030

  日期：2004.10.1

  The hydrido metal carbonyl HRe(CO)5 reacts rapidly with the cluster Rh4(CO)12 at room temperature in n-hexane solvent under CO and H2 to give the coordinately saturated dinuclear carbonyl complex RhRe(CO)9. At room temperature and low partial pressures of CO and H2 (Pi < 2.2 MPa), an observable equilibrium is established between the reactants:  4HRe(CO)5 + Rh4(CO)12 + 4CO → 4RhRe(CO)9 + 2H2. This observation

  的氢基羰基金属H请（CO）5层迅速与簇发生反应的Rh 4（CO）12在室温下在Ñ CO和H下己烷溶剂2，得到配位的双核饱和羰基络合物RhRe（CO）9。在室温和较低的CO和H 2分压（P i <2.2 MPa）下，在反应物之间建立了可观察到的平衡：4HRe（CO）5 + Rh 4（CO）12 + 4CO→4RhRe（CO）9 + 2H 2。该观察结果暗示了分子氢在RhRe（CO）9上的活化作用在温和条件下和在CO的存在下，通过BTEM分析从平衡溶液的原位FTIR光谱测量中获得了RhRe （CO）9的纯组分光谱。新物种的最大吸光度为1985.6（s），2012.2（w），2026.6（vs，br），2075（s）和2127.2（w）cm - 1，表明-Rh（CO ）4部分和-Re（CO）5部分上的正方形双锥体几何形状。温度间隔T = 289.7−308.2 K和分压间隔0.2 MPa < P
• Reactions involving transition metals
  作者：Brian L. Booth、Sylvia Casey、Robert N. Haszeldine

  DOI：10.1016/s0022-328x(00)83411-7

  日期：1982.3

  Ir(CO)2(PPh3)2, Rh(CO)2(PPh3)2), but the use of an excess of [Fe(CO)2(η-C5H6)]− leads to substitution of one fluorine atom on each of the double bonds. The complex having M = Mn(CO)5 reacts with [Pt(PPh3)4] to afford the derivative [(C7F7)Mn(CO)4(PPh3)}Pt(PPh3)2}], and the compound where M = Ir(CO)2(PPh3)2 undergoes an oxidative addition reaction with acetyl chloride. Oxidative coupling products have been

  全氟降冰片二烯与化合物[M（PPh 3）4 ]（M = Pt，Pd）和[IrCl（CO）（PMePh 2）2 ]反应生成加合物[（C 7 F 8）M（PPh 3）2 ] [[C 7 F 8 ] IrCl（CO）（PMePh 2）2 ]，其中一个双键与金属原子配位。铂络合物与[Pt（PPh 3）4 ]进一步反应，生成[（C 7 F 8）Pt（PPh 3）2 } 2具有两个与Pt原子配位的双键的]。所述carbonylmetal阴离子[M - ]反应形成单取代产物[（C 7 ˚F 7）M]（M =锰（CO）5中，Re（CO）5，IR（CO）2（PPH 3）2，的Rh（CO）2（PPH 3）2），但使用过量的[Fe（CO）中的2（η-C 5 H ^ 6）] -导致在每个双键中的一个氟原子的取代。M = Mn（CO）5的配合物与[Pt（PPh 3）4]得到衍生物[（C 7 F 7）Mn（CO）4（PPh
• Solid-State Nuclear Magnetic Resonance Spectroscopic and Quantum Chemical Investigation of ¹³C and ¹⁷O Chemical Shift Tensors, ¹⁷O Nuclear Quadrupole Coupling Tensors, and Bonding in Transition-Metal Carbonyl Complexes and Clusters
  作者：Renzo Salzmann、Martin Kaupp、Michael T. McMahon、Eric Oldfield

  DOI：10.1021/ja973159t

  日期：1998.5.1

  The carbon-13 and oxygen-17 nuclear magnetic resonance spectroscopic shielding behavior, as well as the oxygen-17 nuclear quadrupole coupling constants (NQCC), in the four metal−CO systems Fe(CO)5, Fe2(CO)9, Ni2(η5-C5H5)2(CO)2, and Rh6(CO)16 have been investigated both experimentally and by density functional calculations. Characteristics of the spectroscopic observables and bonding for the most common

  四种金属-CO 系统 Fe(CO)5、Fe2(CO)9、Ni2 中的碳 13 和氧 17 核磁共振光谱屏蔽行为，以及氧 17 核四极耦合常数 (NQCC) (η5-C5H5)2(CO)2 和 Rh6(CO)16 已经通过实验和密度泛函计算进行了研究。因此，可以详细比较最常见的金属-羰基配位类型 μ1-、μ2- 和 μ3-CO 的光谱可观察量和键合的特征。理论预测和实验测量之间通常有很好的一致性，包括先前对 Fe2(CO)9 和 Rh6(CO)16 的 17O 位移预测。有趣的是，Fe2(CO)9 中的桥接氧位移张量具有平行于 CO 轴的最大去屏蔽分量。这对于羰基配体来说是非常不寻常的，但这是在有机羰基中看到的正常行为。为了解释这一现象和其他观察结果，计算出的屏蔽张量和电场梯度...
• Salts of Anionic Metal Carbonyl Clusters with Cryptand[2.2.2](Na⁺ ), DB-18-crown-6(Na⁺ ), and Paramagnetic Cp*₂ Cr⁺ Cations Obtained by Reduction
  作者：Dmitri V. Konarev、Alexey V. Kuzmin、Roman S. Galkin、Salavat S. Khasanov、Rinat F. Kurbanov、Akihiro Otsuka、Hideki Yamochi、Hiroshi Kitagawa、Rimma N. Lyubovskaya

  DOI：10.1002/zaac.201800463

  日期：2019.2.28

  characterized. The increase of nuclearity of clusters under reduction was shown. Fe3(CO)12 preserves the Fe3 core under reduction forming the [Fe3(CO)11]2– dianions in 7. The [CpMo(CO)3]2 and [Mn(CO)5]2 dimers dissociate under reduction forming mononuclear [CpMo(CO)3]– (8) and [Mn(CO)5]– (9) anions. In all anions the increase of negative charge on metal atoms shifts the bands attributed to carbonyl C–O

  中性金属簇（Co 4（CO）12，Ru 3（CO）12，Fe 3（CO）12，Ir 4（CO）12，Rh 6（CO）16，CpMo（CO）3 } 2，研究了在有隐穴[2.2.2]和DB-18-crown-6存在下，由十甲基二茂铬（Cp * 2 Cr）或芴酮酮基制得的Mn（CO）5 } 2）。九种具有顺磁性Cp * 2 Cr +，穴状[2.2.2]（Na +）和DB-18-crown-6（Na +）阳离子和[Co6（CO）15 ] 2-（1，2），的[Ru 6（CO）18 ] 2-（3 - 4）二价阴离子，铑[Rh 11（CO）23 ] 3-（6）抗衡三，和新的[Ir获得了8（CO）18 ] 2-（5）的二价阴离子并对其结构进行了表征。显示了在减少下的团簇的核数增加。Fe 3（CO）12在还原过程中保留了Fe 3核，形成了[Fe 3（CO）11 ] 7中的2-双阴离子。[CpMo（CO）3