tetrahydridobis(pentamethylcyclopentadienyl)diosmium(III) | 160211-10-9

• 英文名称: tetrahydridobis(pentamethylcyclopentadienyl)diosmium(III)
• 英文别名: [(pentamethylcyclopentadienyl)Os(μ-H)4Os(pentamethylcyclopentadienyl)]；[(η5-C5Me5)Os(μ-H)4Os(η5-C5Me5)]；[(C5Me5)Os(μ-H)4Os(C5Me5)]
• CAS: 160211-10-9；1051325-74-6
• 化学式: C₂₀H₃₄Os₂
• 分子量: 654.89
• InChiKey: YRLVCOCIJBOVBU-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：

  四氟硼酸-二乙醚络合物 、 tetrahydridobis(pentamethylcyclopentadienyl)diosmium(III) 以 二氯甲烷 为溶剂， 以98%的产率得到[(C5Me5)Os(H)5Os(C5Me5)]BF4
  参考文献：
  名称：

  三核锇Polyhydrido簇的合成[{（C 5我5）O的} 3（μ-H）6 ] +和{（C 5我5）O的} 3（μ-H）3（μ 3 -H）2和与钌类似物的比较

  摘要：

  在这项研究中，合成了新颖的tri三核多氢配合物。用四氟硼酸对二氢四氢化物络合物（C 5 Me 5）Os（μ-H）4 Os（C 5 Me 5）（4）进行质子化，选择性地提供了新颖的单阳离子五氢物种[（C 5 Me 5）Os（H） ）5 Os（C 5 Me 5）] +（5），而相应的四氢化钌（C 5 Me 5）Ru（μ-H）4 Ru（C 5 Me 5）（3），通过形成中间体阳离子型六氢化二钌（[C 5 Me 5）形成单阳离子六氢化三钌[{（C 5 Me 5）Ru} 3（μ-H）6 ] +（1）。Ru（H）6 Ru（C 5 Me 5）] 2+。双核单阳离子络合物5用作合成the的三核多氢络合物的原料。的反应5与（C 5我5）OSH 5在二氯甲烷中导致三核阳离子[{（C 5 Me 5）Os} 3（μ-H）6 ] +（6）的形成，并转化为{（C 5 Me 5 O）} 3（μ-H ）3（μ 3 -H）

  DOI：

  10.1021/om8003866
• 作为产物：
  描述：

  (η5-pentamethylcyclopentadienyl)pentahydridoosmium 以 苯 为溶剂， 生成 tetrahydridobis(pentamethylcyclopentadienyl)diosmium(III)
  参考文献：
  名称：

  Synthesis and Characterization of Osmium Polyhydrides. X-ray Crystal Structures of (C₅Me₅)OsH₅ and (C₅Me₅)₂Os₂H₄

  摘要：

  Treatment of (C5Me5)(2)Os2Br4 with LiAlH4 in Et2O followed by addition of MeOH at -78 degrees C affords two products: the osmium(VI) pentahydride (C5Me5)OsH5 and the dinuclear osmium(III) tetrahydride (C5Me5)(2)Os2H4. The X-ray crystal structures reveal that (C5Me5)OsH5 adopts a pseudo-octahedral geometry with one axial and four equatorial hydride ligands, whereas all four hydride ligands in (C5Me5)(2)Os2H4 bridge the osmium-osmium axis. Treatment of (C5Me5)OsH5 with HBF4 center dot Et2O affords the osmium(VIII) hexahydride [(C5Me5)OsH6][BF4], which evidently adopts a classical polyhydride structure, as judged from variable-temperature T-1 studies. Treatment of (C5Me5)OsH5 with tert-butyllithium in the presence of N,N,N',N' ',N' '-pentamethyldiethylenetriamine (pmdeta) affords the osmium(IV) tetrahydride salt [Li(pmdeta)][(C5Me5)OsH4], which is proposed to adopt a four-legged piano stool geometry. IR and NMR studies of the Os-D analogues of these new osmium hydrides are also discussed.

  DOI：

  10.1021/om060920b

文献信息

• Synthesis of Heterometallic Trinuclear Polyhydrido Clusters Containing Ruthenium and Osmium and Their Electronic and Structural Deviation from Homometallic Systems
  作者：Hajime Kameo、Takanori Shima、Yumiko Nakajima、Hiroharu Suzuki

  DOI：10.1021/om801222h

  日期：2009.4.27

  A trinuclear heterometallic pentahydrido complex, (Cp*Ru)2(Cp*Os)(μ-H)5 (3), was synthesized by dehydrogenative coupling between a diruthenium tetrahydride complex, Cp*Ru(μ-H)4RuCp*, and an osmium pentahydride, Cp*OsH5; an analogous complex, (Cp*Ru)(Cp*Os)2(μ-H)5 (4), was obtained by the reaction of a dimeric ruthenium methoxo complex, Cp*Ru(μ-OMe)2RuCp*, with a diosmium tetrahydride complex, Cp*Os(μ-H)4OsCp*

  三核杂金属pentahydrido络合物，（CP * Ru）的2（CP * OS）（μ-H）5（3），通过脱氢偶联一个二钌四氢化络合物中，CP *茹（μ-H）之间的合成4 RuCP *，五氢化CP * OSH 5；通过二聚钌甲氧基络合物CP * Ru（μ-OMe）2 RuCP *的反应得到类似物（CP * Ru）（CP * OS）2（μ-H）5（4）在氢的大气压下，四氢化二di络合物CP * OS（μ-H）4 OSCP *。配合物3和4具有足够的碱性，可以被HBF质子化如图4所示，导致形成相应的六氢阳离子，[（CP * Ru）2（CP * OS）（μ-H）6 ] +（7）和[（CP * Ru）（CP * OS）2（μ- H）6 ] +（8）。在两个杂金属体系7和4之间进行质子转移的实验表明，RuOS 2五氢化物比Ru 2 OS五氢化物更碱性。优化了异金属polyhydrido复合物的结构3，4，7，和8使用它们的C推导5
• Reaction of a Heterobimetallic Polyhydrido Cluster, [Cp*Ru(μ-H)₄OsCp*] (Cp* = η⁵-C₅Me₅), with Diphenylacetylene. Regioselective C−H Bond Activation at the Osmium Center
  作者：Takanori Shima、Toshiaki Ichikawa、Hiroharu Suzuki

  DOI：10.1021/om700606q

  日期：2007.12.1

  The reactivity of a heterobimetallic polyhydrido complex [Cp*Ru(mu-H)(4)OsCP*] (1) toward diphenylacetylene is studied to elucidate the roles of each metal atom in the substrate activation step. The reaction of 1 with an equivalent of diphenylacetylene exclusively produces a eta(2)-trans-stilbene complex [Cp*Ru( mu-H)2(mu-trans-PhHC=CHPh)OsCp*] (8), in which trans-stilbene is coordinated to the osmium metal by way of the)eta(2)-cis-stilbene complex [Cp*Ru(mu-H)2(mu-cis-PhHC=CHPh)OsCp*] (10). Treatment of I with an excess amount of diphenylacetylene yields [Cp*Ru(U-H)(mu-eta(1):eta(2)-cis-PhC=CHPh)(trans-PhHC= C HPh)OsCp*] (11) via complex 8. Intermediacy of 8 in the formation of 11 is confirmed by the reaction of 8 with diphenylacetylene. Themolysis of 11 in C6D6 at 50 degrees C generates a mu-perpendicularly coordinated diphenylacetylene complex [Cp*Ru(mu-H)2(mu-eta(2):eta(2)-PhCCPh)OsCp*] (12) and a benzo-osmacyclopentadiene complex [Cp*Os(mu-PhC=CH-C6H4-)H2RuCp*] (13) together with trans-stilbene. Complex 8 is converted into 13 even in the absence of added diphenylacetylene. Upon heating of 8 in THF, 13 is formed as a result of the C(Sp(2))-H bond cleavage and subsequent intramolecular activation of the C(ortho)-H bond at the osmium center. The molecular structures Of [(C5Me4Et)Ru(mu-H)2(,mu-trans-PhHC=CHPh)OsCp*] (8'), [(C5Me4Et)Ru(mu-H)(mu-eta 1:eta 2-cis-PhC=CHPh)(trans-Ph HC=CHPh)OsCp*] (11'), 12, [Cp*Os(mu-PhC= CH-C6H4-)H2Ru(C5Me4Et)] (13') and [Cp*Os(mu-PhC=CH-C6H4-)H2OSCP*] (15) are determined by X-ray studies.