[(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(benzene-1,2-dithiolate)] | 203303-60-0

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: [(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(benzene-1,2-dithiolate)]
• 英文别名: [Cp*Rh(benzene-1,2-dithiolate)]；(η(5)-pentamethylcyclopentadienyl)Rh(1,2-benzenedithiolate)；[Cp*Rh(1,2-benzenedithiolate)]；[(η5-C5Me5)Rh(1,2-benzenedithiolate))]；[(η5-C5Me5)Rh(S2C6H4)]；(η5-C5Me5)Rh(SSC6H4)；benzene-1,2-dithiolate;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(3+)
• CAS: 203303-60-0
• 化学式: C₁₆H₁₉RhS₂
• 分子量: 378.364
• InChiKey: ZFUGSMWLGSDFPS-UHFFFAOYSA-L

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：

  tricarbonyltris(pyridine)molybdenum 、 [(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(benzene-1,2-dithiolate)] 在 BF₃*Et₂O 作用下， 以 甲苯 为溶剂， 生成 [(η5-C5Me5)Rh(S2C4H6))2Mo(CO)2]
  参考文献：
  名称：

  Rh−Mo−Rh 二硫醇络合物的双电子还原形成与 CO 配位模式变​​化相关的三重基态

  摘要：

  我们合成了一种二硫醇桥连的异金属三核配合物 [{(eta(5)-C(5)Me(5))Rh(S(2)C(6)H(4))}(2)Mo(CO)( 2)] (1) 其中两个红二硫烯复合单元由 Mo(CO)(2) 部分桥接。具有 Rh(III)-Mo(0)-Rh(III) 键的配合物 1 表现出可逆的一步两电子还原和电位反转。1 和 1(2-) 之间的这种氧化还原过程伴随着可逆的结构变化，这是 CO 协调模式在半桥接和桥接之间的交替。具有 Rh(II)-Mo(0)-Rh(II) 键的二价阴离子 1(2-) 的基态被指定为自旋三重态。CO配位模式和自旋态的这些变化与密度泛函理论计算结果完全一致。

  DOI：

  10.1021/ja8090577
• 作为产物：
  描述：

  [(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(benzene-1,2-dithiolate)]2 以 二氯甲烷 为溶剂， 生成 [(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(benzene-1,2-dithiolate)]
  参考文献：
  名称：

  Synthesis and characterization of pentamethylcyclopentadienylrhodium(III) and -iridium(III) complexes with 1,2-benzenedithiolate · [(Cp∗Rh)2(μ(S)-1,2-C6H4S2-S,S′)2], [(Cp∗Rh)2(μ(S)-1,2-C6H4S2-S,S′)(μ(S)-1,2-C6H4S(SO2)-S,S′)] and [(Cp∗Ir)(1,2-C6H4S2-S,S′)] () Professor Peter M. Maitlis on the occasion of his 65th birthday and in recognition of his pioneer contributions to this field

  摘要：

  A reaction of the triple cubane-type organometallic polyoxomolybdate cluster, [(Cp * Rh)(4)Mo4O16]. 2H(2)O (1 . 2H(2)O), with 1,2-benzenedithiol gives a 1,2-benzenedithiolate-bridged dinuclear complex, [(Cp * Rh)(2)(mu(S)-1,2-C6H4S2-S,S')(2)] (2), and another dinuclear complex, [(Cp * Rh)(2)(mu(S)-1,2-C6H4S2-S,S')(mu(S)-1,2-C6H4S(SO2)-S,S')] (3), both of which are characterized by the single-crystal X-ray diffraction method. The former complex, 2, is also obtained from a reaction of [(Cp * RhCl)(2)(mu-Cl)(2)] with 1,2-benzenedithiol in the presence of NaOCH3, and the latter, 3, from oxygenation of 2 with t-BuOOH. The H-1 NMR study in CD2Cl2 indicates that complex 2 changes gradually to a coordinatively unsaturated mononuclear complex, [Cp * Rh(1,2-C6H4S2-S,S')] (4). An analogous mononuclear iridium(III) complex, [Cp * Ir(1,2-C6H4S2-S,S')] (5), is also prepared and characterized by X-ray structural analysis. (C) 1997 Elsevier Science S.A.

  DOI：

  10.1016/s0022-328x(97)00473-7

文献信息

• Synthesis and Reactivity of a Dithiolate-Bridged Ruthenium−Rhodium Heterobimetallic Dihydride Complex
  作者：Shin Takemoto、Daisuke Shimadzu、Ken Kamikawa、Hiroyuki Matsuzaka、Ryoki Nomura

  DOI：10.1021/om050871n

  日期：2006.2.1

  dihydride complex [Cp*Rh(μ2-1,2-S2C6H4)(μ2-H)RuH(PPh3)2] (2) upon treatment with KOH/i-PrOH. Complex 2 reacts with CO to give the dicarbonyl complex [Cp*Rh(μ2-1,2-S2C6H4)Ru(CO)2(PPh3)] (3). Reaction of 2 with p-tolylacetylene (2 equiv) proceeds with hydrogenation of the alkyne and subsequent oxidative addition of the sp C−H bond to give the alkynyl hydride complex [Cp*Rh(μ2-1,2-S2C6H4)(μ2-H)Ru(C⋮CTol-p)(PPh3)2]

  新的二硫醇盐桥联的Ru-铑的异二氢化复杂的[CP *的Rh（μ 2 -1,2-S 2 C ^ 6 ħ 4）（μ 2 -H）期RuH（PPH 3）2 ]（2）已被制备，并研究了其与一氧化碳和炔烃的反应。铑1,2- benzenedithiolate复杂的[CP *的Rh（1,2--S的治疗2 ç 6 ħ 4）]（CP * =η 5 -C 5我5）与[RuHCl（PPH 3）3 ]在THF产生氢化物和二硫醇-桥连的Ru-的Rh的异复杂的[CP *的Rh（μ 2 -1,2-S2 ç 6 ħ 4）（μ 2 -H）的RuCl（PPH 3）2 ]（1），将其进一步转化为二氢化物配合物的[CP *的Rh（μ 2 -1,2-S 2 C ^ 6 ħ 4） （μ 2 -H）期RuH（PPH 3）2 ]（2）在用KOH /治疗我的i-PrOH。复杂2种发生反应与CO，得到的二羰基配合物的[CP *的Rh（μ 2
• Thermochromic Triangular [MCo₂] (M = Rh, Ir, Ru) Clusters Containing a Planar Metalladithiolene Ring in η³ Coordination
  作者：Norikiyo Nakagawa、Teppei Yamada、Masaki Murata、Manabu Sugimoto、Hiroshi Nishihara

  DOI：10.1021/ic051829n

  日期：2006.1.1

  The first series of triangular cluster complexes of [MCo(2)] (M = Rh, Ir, Ru) with a planar metalladithiolene ring coordinating in the eta(3)-bonding mode were synthesized, and the crystal structures, spectral and electrochemical properties, and thermochromism of these complexes were revealed.

  合成了第一系列的[MCo（2）]（M = Rh，Ir，Ru）的三角形簇络合物，其具有在eta（3）-键模式下配位的平面金属二硫代噻吩环，并且其晶体结构，光谱和电化学性质，并揭示了这些配合物的热致变色现象。
• Benzenedithiolate-bridged Rh₂W and RhW Cluster Complexes: Synthesis, Properties, and Formation Mechanism
  作者：Satoru Tsukada、Ryota Sakamoto、Hiroshi Nishihara

  DOI：10.1246/cl.2012.357

  日期：2012.4.5

  [Cp*Rh(S2C6H4)}2W(CO)2] (Cp*: η5-C5Me5) (1) and [Cp*Rh(S2C6H4)}(S2C6H4)W(CO)2] (2) were synthesized by the reaction of rhodadithiolene [Cp*Rh(S2C6H4)] with [W(CO)3(py)3], and their crystal structures and physical properties were investigated. The formation mechanism of 2 from 1 was pursued by 1H NMR spectroscopy. 1 reacted with an excess amount of BF3·Et2O to furnish 2, indicating that a Lewis acid assisted the demetalation reaction.

  通过将二茂铑[Cp*Rh(S2C6H4)]与三(吡啶)三(三氟甲烷磺酸)钨[W(CO)3(py)3]反应，合成了[Cp*Rh(S2 )}2W(CO)2] (Cp*: η5-C5Me5) (1)和[Cp*Rh(S2 )}(S2 )W(CO)2] (2)，并对其晶体结构和物理性质进行了研究。通过1H NMR光谱研究了1到2的形成机理。1与过量的三氟甲烷磺酸乙酯反应生成2，表明路易斯酸促进了脱金属反应。
• Dithiolato‐Bridged [MRu ₂ ] (M = Rh, Ir, Ru) Triangular 50e ^– Cluster Complexes Synthesized by Complete Metal Framework Reconstruction
  作者：Norikiyo Nakagawa、Masaki Murata、Manabu Sugimoto、Hiroshi Nishihara

  DOI：10.1002/ejic.200600255

  日期：2006.6

  A method for synthesizing triangular dithiolene-bridged trinuclear cluster complexes [LM(S2C6H4)}Ru2(CO)4(S2C6H4)] [M = Rh, L = (η5-C5Me5); M = Ir, L = (η5-C5Me5); M = Ru, L = (η6-C6Me6)] by complete reconstruction of the metal framework was developed. The complexes thus obtained have 50 electrons around the metal atoms, indicating 3c4e– bonds; their molecular structures were determined by X-ray diffraction

  一种合成三角二硫烯桥连三核簇配合物的方法[LM(S2C6H4)}Ru2(CO)4(S2 )][M=Rh,L=(η5-C5Me5); M = Ir，L = (η5-C5Me5)；M = Ru, L = (η6-C6Me6)] 通过完全重建金属框架而开发。这样得到的配合物在金属原子周围有 50 个电子，表明是 3c4e-键；它们的分子结构是通过 X 射线衍射分析和理论计算确定的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)