η5-pentamethylcyclopentadienyl[1,2-dicarba-closo-dodecaborane(12)-diselenolato]rhodium | 251316-71-9

• 英文名称: η5-pentamethylcyclopentadienyl[1,2-dicarba-closo-dodecaborane(12)-diselenolato]rhodium
• 英文别名: (pentamethylcyclopentadienyl)Rh(1,2-dicarba-closo-dodecaborane(12)-1,2-diselenolate)；(C5Me5)Rh(1,2-dicarba-closo-dodecaborane(12)-1,2-diselenolato)；(η5-pentamethylcyclopentadienyl)Rh[1,2-dicarba-closo-dodecaborane-1,2-diselenolato]；[(η5-C5Me5)Rh(1,2-dicarba-closo-dodecarborane-1,2-diselenolato)]；[(η5-pentamethylcyclopentadienyl)Rh(Se2C2B10H10)]；(Cp*)Rh(Se2C2B10H10)
• CAS: 251316-71-9
• 化学式: C₁₂H₂₅B₁₀RhSe₂
• 分子量: 538.266
• InChiKey: OBDNHPGFMLXZMV-UHFFFAOYSA-N

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：

  carbon monoxide,cobalt,cyclopenta-1,3-diene 、 η5-pentamethylcyclopentadienyl[1,2-dicarba-closo-dodecaborane(12)-diselenolato]rhodium 在 Me₃NO 作用下， 以 甲苯 为溶剂， 以46%的产率得到((η5-pentamethylcyclopentadienyl)Rh)((η5-cyclopentadienyl)Co)[1,2-dicarba-closo-dodecaborane-1,2-diselenolato]
  参考文献：
  名称：

  A facile and general approach to the Rh–M (M = Co, Rh) single bond supported by ortho-carborane-1,2-dichalcogenolato ligands

  摘要：

  通过Cp*Rh[E2C2(B10H10)] (E = S (1a), Se (1b)) 和 CpRh[S2C2(B10H10)] (2a) 与低价半夹心CpCo(CO)2或CpRh(C2H4)2在适度条件下的反应，合成了一系列具有直接金属-金属相互作用的异核和同核双金属络合物。所得到的产物，即（Cp*Rh)(CpCo)[E2C2(B10H10)] (E = S(3a); Se(3b))， （Cp*Rh)(CpRh)[E2C2(B10H10)] (E = S(4a); Se(4b)) 和 （CpRh)(CpRh)[S2C2(B10H10)] (5a)，通过红外光谱（IR）、核磁共振（NMR）和元素分析进行了全面表征。3a、3b、4a、4b和5a的分子结构通过X射线晶体学分析得到确认，Rh–Co键（2.4778(11) (3a) 和 2.5092(16) (3b) Å）和Rh–Rh键（2.5721(8) (4a)，2.6112(10) (4b)，2.5627(10) (5a) Å）均处于单键范围内。

  DOI：

  10.1039/b617295d
• 作为产物：
  描述：

  dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 dilithium 1,2-dicarba-closo-dodecaborane(12)-1,2-diselenolate 以 四氢呋喃 、 乙醚 为溶剂， 生成 η5-pentamethylcyclopentadienyl[1,2-dicarba-closo-dodecaborane(12)-diselenolato]rhodium
  参考文献：
  名称：

  含1,2-二硫代碳硼烷或碳酸根配体的双核半三明治铱和铑碳烯配合物的合成与表征

  摘要：

  双-NHC配体与16电子半夹心式Ir和Rh二卤代原烟酸酯碳硼烷络合物Cp * M [E 2 C 2（B 10 H 10）]（M = Ir，Rh; E = S，Se）或16的反应-电子半三明治式Ir和Rh碳酸盐复合物Cp * M（μ-O）2 CO（M = Ir，Rh）得到相应的18电子双核复合物，类型为[{Cp * M（E 2 C 2（B 10 H 10））} 2 L]（L = 1,1'-（1,2-乙二基）双（3-甲基咪唑啉-2-亚基）； M = Ir，E = S（4a），Se（4b）； M = Rh，E = S（5a），Se（5b））和[Cp * M（μ-O）2CO] 2 L（M = Ir（8），Rh（9））。配合物4 - 9也可以从混合[Cp *的MC1的反应直接得到2 ] 2 L（M =铱（2），铑（3））与Li 2 [E 2 Ç 2（B 10 H ^ 10）]或Na 2 CO 3高收

  DOI：

  10.1021/om800694h
• 作为试剂：
  描述：

  二茂铁乙炔 、 氯仿 在 η5-pentamethylcyclopentadienyl[1,2-dicarba-closo-dodecaborane(12)-diselenolato]rhodium 作用下， 以 氯仿 为溶剂， 以10%的产率得到
  参考文献：
  名称：

  The reaction of ethynylferrocene with Cp*Rh half-sandwich complexes containing a chelating 1,2-dicarba-closo-dodecaborane(12)-1,2-dichalcogenolato ligand, Cp*Rh[E2C2(B10H10)], E=S, Se

  摘要：

  Dimerisation of ethynylferrocene (2) to give a mixture of (E)- and (Z)-1,4-diferrocenylbuten-3-yne (ratio = 1.1) takes place in boiling chloroform if the 16e half-sandwich complex Cp*Rh[Se2C2(B10H10)] (1Se) is present. Under these conditions cyclo-trimerisation was not observed. In contrast, Cp*Rh[S2C2(B10H10)] (1S) reacts with 2 in a 1:1 ratio by insertion into one of the Rh-S bonds, followed by B-H activation, transfer of a hydrogen atom to carbon via rhodium and formation of a Rh-B bond to give 7S which was characterised by an X-ray structural analysis. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00673-2

文献信息

• Synthesis and structure of heterometallic complexes (RhFe, CoFe) containing bridging 1,2-dicarba-closo-dodecarborane-1,2-dichalcogenolato ligands
  作者：Shuyi Cai、Xiu-Feng Hou、Yin-Qiang Chen、Guo-Xin Jin

  DOI：10.1039/b607195c

  日期：——

  The prototype hetero-binuclear complexes containing metal-metal bonds, CpRh[E2C2(B10H10)]}[Fe(CO)3] (Cp = Cp* = eta 5-Me5C5, E = S(5a), Se(5b); Cp = Cp = eta 5-1,3-tBu2C5H3, E = S(6a), Se(6b)) and CpCo[E2C2(B10H10)]}[Fe(CO)3] (Cp = Cp* = eta 5-Me5C5, E = S(7a), Se(7b); Cp = Cp = eta 5-C5H5, E = S(8a), Se(8b)) were obtained from the reactions of 16-electron complexes CpRh[E2C2(B10H10)] (Cp = Cp*, E

  包含金属-金属键CpRh [E2C2（B10H10）]} [Fe（CO）3]的原型异双核络合物（Cp = Cp * = eta 5-Me5C5，E = S（5a），Se（5b） ; Cp = Cp = eta 5-1,3-tBu2C5H3，E = S（6a），Se（6b））和CpCo [E2C2（B10H10）]} [Fe（CO）3]（Cp = Cp * = eta 5-Me5C5，E = S（7a），Se（7b）; Cp = Cp = eta 5-C5H5，E = S（8a），Se（8b））由16电子配合物CpRh [E2C2 （B10H10）]（Cp = Cp *，E = S（1a），Se（1b）； Cp = Cp，E = S（2a），Se（2b）），CpCo [E2C2（B10H10）]（Cp = Cp *，E = S（3a），Se（3b）; Cp = Cp，E = S（4a），
• Heterometallic cluster complexes (RhMo, RhW) containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalocogenolato ligands
  作者：Shuyi Cai、YueJian Lin、Guo-Xin Jin

  DOI：10.1039/b511096c

  日期：——

  half-sandwich rhodium complex [Cp*RhE2C2(B10H10)}] [Cp* = η5-C5Me5, E = S (1a), Se (1b)] [Cp*RhE2C2(B10H10)} = η5-pentamethylcyclopentadienyl[1,2-dicarba-closo-dodecaborane(12)-dichalcogenolato]rhodium] reacted with Mo(CO)3(py)3 in the presence of BF3·Et2O in THF solution to afford the Cp*Rh[E2C2(B10H10)]}2Mo(CO)2 (E = S (3a); Se (3b)), Cp*Rh[S2C2(B10H10)]}Mo(CO)2[S2C2(B10H10)]} (4). The voluminous

  16电子半夹心铑配合物的[Cp *铑ë 2 Ç 2（B 10 H ^ 10）}]的[Cp * =η 5 -C 5我5，E = S（1A），硒（1B）]的[Cp *铑ë 2 ç 2（B 10 H ^ 10）} =η 5 -五甲基咪唑并[1,2-dicarba-闭合碳-dodecaborane（12）-dichalcogenolato]铑]以Mo（CO）反应3（PY）3在BF 3 ·Et 2 O在THF溶液中存在，得到Cp * Rh [E 2 C2（B 10 H 10）]} 2 Mo（CO） 2（E = S（ 3a）; Se（ 3b）），Cp * Rh [S 2 C 2（B 10 H 10）]} Mo（CO ） 2 [S 2 C 2（B 10 H 10）]}（ 4）。大量的二叔丁基取代的Cp半三明治铑配合物[Cp'Rh E 2 C 2（B 10 H 10）}] [E = S（ 2a），Se（
• Reactivity of Cp*Rh 16e Half-Sandwich Complexes Containing a Chelating 1,2-Dicarba-<i>closo</i>-dodecaborane-1,2-dichalcogenolato Ligand. Intermediates in the Catalyzed Trimerization of Methyl Acetylene Carboxylate and Phenylacetylene
  作者：Max Herberhold、Hong Yan、Wolfgang Milius、Bernd Wrackmeyer

  DOI：10.1021/om0003077

  日期：2000.10.1

  toluene. In boiling chloroform or at room temperature in dichloromethane, trimerization is of minor importance. In the case of 1Se and methyl acetylene carboxylate, an intermediate 3Se, formed in the course of the trimerization process, could be characterized by X-ray structural analysis. The dimer 2Se catalyzes trimerization in the same way as 1Se. In the absence of HC⋮C−CO2Me, 2Se rearranges upon

  研究了16电子（16e）半三明治复合物Cp * Rh [E 2 C 2（B 10 H 10）] [E = S（1S），Se（1Se）]与甲基乙炔羧酸酯和苯乙炔的反应。为了获得有关初级加成产物和炔烃潜在的催化低聚反应（根据反应条件的函数）的信息。铑配合物1S和1Se在温和条件下均与HC⋮C-CO 2 Me反应生成低产率的二聚体2S和2Se，其中2Se可以通过X射线结构分析表征。两个都1S和1Se用作HC⋮C-CO 2 Me和HC⋮C-Ph环化三聚反应的催化剂，如果比例为1：1，则分别生成1,3,5-和1,2,4-三取代苯反应在70℃下在甲苯中进行。在沸腾的氯仿中或室温下的二氯甲烷中，三聚化的重要性较小。在1Se和甲基乙炔羧酸酯的情况下，可以通过X射线结构分析来表征在三聚过程中形成的中间体3Se。二聚体2Se以与1Se相同的方式催化三聚。在没有HC⋮C-CO 2 Me，2Se的情况下在70°C
• 16- and 18-Electron Cp*Rh complexes with 1,2-dicarba-closo-dodecaborane(12)-1,2-dichalcogenolato ligands, as studied by multinuclear magnetic resonance
  作者：M Herberhold

  DOI：10.1016/s0022-328x(99)00330-7

  日期：1999.9.25

  The reaction of [Cp*RhCl2](2) 1 with dilithium 1,2-dicarba-closo-dodecaborane(12)-1,2-dithiolate (a) and -diselenolate (b) afforded the 16-electron rhodium(III) half-sandwich complexes Cp*Rh[E2C2(B10H10)] [E=S (3a), Se (3b)]. The 18-electron trimethylphosphane rhodium(III) half-sandwiches Cp*Rh(PMe3)[E2C2(B10H10)] 4a-c were prepared from the reaction of Cp*RhCl2(PMe3) 2 with the same dichalcogenolates, including the ditelluride (c). The complexes 4a,b could also be obtained from the reaction of 3a,b with trimethylphosphane. The molecular geometry of 4b was determined by X-ray structural analysis. The 16-electron complexes 3 an monomeric in solution as shown by multinuclear magnetic resonance (H-1-, B-11-, C-13-, P-31- Se-77-, Rh-103-, Te-125-NMR). also in comparison with the data for the trimethylphosphane analogues 4a-c and for 6a in which the rhodium bears the eta(5)-1,3-C5H3 Bu-t(2) ligand. The Rh-103 nuclear shielding is reduced by 831 ppm (3a) and 1114 ppm (3b) with respect to the 18-electron complexes 4a,b. Similarly, the Se-77 nuclear shielding in 3b is reduced by 676.4 ppm with respect to that in 4b. (C) 1999 Elsevier Science S.A. All rights reserved.
• Heteronuclear Tungsten and Cobalt Derivatives of the 16-Electron Half-Sandwich Complex Cp*Rh[E₂C₂(B₁₀H₁₀)] (E = S, Se)
  作者：Shuyi Cai、Guo-Xin Jin

  DOI：10.1021/om050598p

  日期：2005.10.1

  The 16-electron half-sandwich rhodium complex [Cp*RhE2C2(B10H10)}] [E = S (1a), Se (1b)] (Cp* = eta(5)-C5Me5) reacted with W(CO)(3)(py)(3) in the presence of BF3 center dot Et2O in THF solution to afford Cp*Rh[E2C2(B10H10)]}(2)W(CO)(2) (E = S (2a); Se (2b)), (Cp*Rh)(2)[S2C2(B10H10)] (3), CP*Rh[S2C2(B10H10)]W(CO)(2)[S2C2(B10H10)] (4), and Cp*Rh(CO)[Se2C2(B10H10)]W(CO)(5) (5). The trinuclear clusters Cp*Rh[E2C2(B10H10)}[CO2(CO)(5)] [E = S (6a), Se (6b)] were obtained from the reactions of 1a and 1b with CO2(CO)(8) in the presence of Me3NO. The complexes have been fully characterized by IR and NMR spectroscopy as well as by element analyses. The X-ray crystal structures of complexes 2-6 are reported.