Os(hydride)6(triisopropylphosphine)2 | 131296-74-7

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: Os(hydride)6(triisopropylphosphine)2
• 英文别名: Os(H)6(P(i)Pr3)2；osmium hexahydride;tri(propan-2-yl)phosphane
• CAS: 131296-74-7
• 化学式: C₁₈H₄₈OsP₂
• 分子量: 516.727
• InChiKey: UVZBAEMKZRNNIK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.78
• 重原子数：
  21.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  Os(hydride)6(triisopropylphosphine)2 、 2-苯基苯并咪唑 以 甲苯 为溶剂， 反应 6.0h， 以60%的产率得到
  参考文献：
  名称：

  Azole Assisted C–H Bond Activation Promoted by an Osmium-Polyhydride: Discerning between N and NH

  摘要：

  The capacity of the hexahydride complex OsH6((PPr3)-Pr-i)(2) (1) to discern between the nitrogen atom and the NH unit in the azole assisted aryl C-H bond activation has been investigated. Complex 1 reacts with 2-phenylimidazole to give OsH3{kappa(2)-C,N-(C6H4-imidazole)}((PPr3)-Pr-i)(2) (2), which has been characterized by X-ray diffraction analysis. The structure proves the higher affinity of the metal center for the N atom in the presence of the NH unit, which remains unchanged, and reveals that in the solid state the molecules of this complex form infinite chains by means of intermolecular asymmetric 3-center bifurcated dihydrogen bonds. In solution, H-1-DOSY NAIR. experiments suggest that the association degree decreases as the temperature increases. The fused six-membered ring of benzimidazole weakens the NH bond, enhancing its reactivity. As a consequence, complex 1 cannot discern between the N atom and the NH unit of 2-phenylbenzimidazole. Thus, the treatment of 1 with this substrate leads to a mixture of OsH3{kappa(2)-C,N-(C6H4-benzimidazole)}((PPr3)-Pr-i)(2) (3) and the dinuclear species ((PPr3)-Pr-i)(2)H3Os(C6H4-benzimidazolate)OsH(eta(2)-H-2)((PPr3)-Pr-i)(2) (4). The latter is the result of a N-assisted ortho-C-H bond activation of the phenyl group promoted by 0.5 equiv of I and the N-H bond activation promoted by the remaining 0.5 equiv of hexahydride 1 along with the agostic coordination of the remaining ortho-C-H bond to the metal center of the unsaturated fragment OsH(eta(2)-H-2) ((PPr3)-Pr-i)(2). The comparison of the redox properties of 3 and 4 suggests that the interaction between the metal centers in the dinudear compound is negligible. The replacement of the NH group of the azoles by a sulfur atom does not modify the behavior of the substrates. Thus, the reactions of 1 with 2-phenylthiazole and 2-phenylbenzothiazole afford OsH3{kappa(2)-C,N-(C6H4-thiazole)}((PPr3)-Pr-i)(2) (5) and OsH3{kappa(2)-C,N-(C6H4-benzothiazole)}((PPr3)-Pr-i)(2) (6). In turn, complexes 2, 3, 5, and 6 are phosphorescent.

  DOI：

  10.1021/acs.organomet.5b00174
• 作为产物：
  描述：

  以 甲醇 为溶剂， 以>99的产率得到Os(hydride)6(triisopropylphosphine)2
  参考文献：
  名称：

  Esteruelas, Miguel A.; Jean, Yves; Lledós, Agustí, Inorganic Chemistry, 1994, vol. 33, # 16, p. 3609 - 3611

  摘要：

  DOI：
• 作为试剂：
  描述：

  丙腈 在 Os(hydride)6(triisopropylphosphine)2 、 水 作用下， 以 氘代四氢呋喃 为溶剂， 反应 2.0h， 以78%的产率得到丙酰胺
  参考文献：
  名称：

  多氢化锇催化的脂肪族腈的水合：替代机制的证据

  摘要：

  六氢化物 OsH 6 (P i Pr 3 ) 2有效地催化脂肪族腈水合为酰胺。催化条件下的主要金属物种是三氢化锇(IV)酰胺化物衍生物OsH 3 {κ 2 - N , O -[HNC(O)R]}(P i Pr 3 ) 2，它们已被分离和充分表征对于 R = i Pr 和t卜。水合速率与催化剂前体、腈和水的浓度成正比。当这些实验结果和密度泛函理论计算相结合时，催化机制已经建立。配合物OsH 3 {κ 2 - N , O -[HNC(O)R]}(P i Pr 3 ) 2解离螯合物的羰基，得到与腈配位的κ 1 - N -酰胺衍生物。随后外部水分子攻击腈的 C(sp) 原子和酰胺化物的 N 原子，得到酰胺并再生 κ 1 - N-酰胺催化剂。该攻击是协同的，并通过循环六元过渡态发生，其中涉及 C腈···O-H···N酰胺相互作用。在攻击之前，κ 1 - N -酰胺配体的游离羰基将水分子固定在腈的 C(sp)

  DOI：

  10.1021/acs.inorgchem.1c00380

文献信息

• Osmium Hydride Acetylacetonate Complexes and Their Application in Acceptorless Dehydrogenative Coupling of Alcohols and Amines and for the Dehydrogenation of Cyclic Amines
  作者：Miguel A. Esteruelas、Virginia Lezáun、Antonio Martínez、Montserrat Oliván、Enrique Oñate

  DOI：10.1021/acs.organomet.7b00521

  日期：2017.8.14

  presence of 5 mol % of KOH, complexes 3–6 promote the coupling of benzyl alcohol and aniline to give N-benzylideneaniline and H2. Under the same conditions, complex 3 catalyzes a wide range of analogous couplings to afford a variety of imines, including aliphatic imines, with yields between 90 and 40% after 1–48 h. Complex 3 also catalyzes the dehydrogenation of cyclic amines. According to the amount

  从OsH 6（P i Pr 3）2（1）和OsH 2 Cl 2（P i Pr 3）2（2）开始制备新的氢化配合物，以及它们在醇和胺的无受体脱氢偶联中的催化活性并报道了环胺的脱氢。配合物1与乙酰丙酮（Hacac）反应，得到经典的三氢化物OsH 3（acac）（P i Pr 3）2（3）。3的质子化用三氟甲磺酸（HOTf）产生H 2的释放并形成不饱和二氢os（IV）[OsH 2（acac）（P i Pr 3）2 ] OTf（4），也可以从2开始通过中间体OsH 2 Cl（acac）（P i Pr 3）2（5）。用KOH处理5的乙酰丙酮溶液，得到Os（acac）2（P i Pr 3）2（6）。在5摩尔％的KOH存在下，络合物3– 6促进苄醇和苯胺的偶联，得到N-苄叉基苯胺和H 2。在相同条件下，配合物3催化多种类似的偶合反应，从而提供各种亚胺，包括脂肪族亚胺，在1–48小时后收率在90％至40％
• ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES
  申请人：Universal Display Corporation

  公开号：US20190088889A1

  公开（公告）日：2019-03-21

  The present invention includes novel heteroleptic/homoleptic iridium complexes containing two tridentate ligands, where at least one of the tridentate ligands comprises of pyridinium-derived N-heterocyclic carbene. The compounds of the present invention may be useful for organic electroluminescent devices.

  本发明包括含有两个三齿配体的新型异配/同配铱配合物，其中至少一个三齿配体由吡啶鎓衍生的N-杂环卡宾组成。本发明的化合物可能对有机电致发光设备有用。
• Osmium Catalysts for Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines: Unusual Coordination Modes of a BPI Anion
  作者：María L. Buil、Miguel A. Esteruelas、M. Pilar Gay、Mar Gómez-Gallego、Antonio I. Nicasio、Enrique Oñate、Alicia Santiago、Miguel A. Sierra

  DOI：10.1021/acs.organomet.7b00906

  日期：2018.2.26

  (11), p-cymene (12)). The electronic structrure and electrochemical properties of the dinuclear complexes were also studied. Complexes 3 and 4 are efficient catalyst precursors for the acceptorless and base-free dehydrogenation of secondary and primary alcohols and cyclic and lineal amines. The primary alcohols afford aldehydes. The amount of H2 released per gram of heterocycle depends upon the presence

  已经发现了用于基于有机液体的氢载体脱氢的新型催化剂前体。配合物OSH 6（P i Pr 3）2（1）和OSH（OH）（CO）（P i Pr 3）2（2）与1,3-双（6'-甲基-2'-吡啶基氨基）异吲哚啉反应（HBMePI），得到OSH 3 κ 2 -N吡啶，N亚胺- （BMePI）}（P我镨3）2（3）和职业安全与卫生κ 2 -N吡啶，N亚胺-（BMePI）}（CO）（P i Pr 3）2（4）。前所未有的κ 2 -N吡啶，N亚胺BMePI的协调模式热力学与锇（IV）和OS（II）的金属碎片优选和允许制备基于BMePI-双核金属阳离子。在KO t Bu存在下，用0.5当量的HBMePI处理OSH 2 Cl 2（P i Pr 3）2（5），得到双OS IV型双核阳离子的氯化物盐[OSH 3（P i Pr 3）2} 2 μ-（κ 2 -N吡啶，N亚胺）2 -BMePI}] +（6）。
• Reactions of an Osmium-Hexahydride Complex with Cytosine, Deoxycytidine, and Cytidine: The Importance of the Minor Tautomers
  作者：Miguel A. Esteruelas、Jorge García-Raboso、Montserrat Oliván

  DOI：10.1021/ic3013238

  日期：2012.9.3

  solutions of 2. Complex 1 is also able to perform the double deprotonation of cytosine (cytosinate′) to afford the dinuclear derivative (PiPr3)2H3Os(cytosinate′)OsH3(PiPr3)2 (3), where the anion is coordinated κ2-N1,O and κ2-N3,N4 to two different OsH3(PiPr3)2 metal fragments. The deprotonation of deoxycytidine and cytidine leads to OsH3(deoxycytidinate)(PiPr3)2 (4) and OsH3(cytidinate)(PiPr3)2 (5),

  复杂的OsH 6（P i Pr 3）2（1）使胞嘧啶去质子化，得到分子氢和d 4-三氢化物衍生物OsH 3（胞嘧啶）（P i Pr 3）2（2），它们在溶液中以以下形式混合存在：含有κ异构体2 -N1，O（2A）和κ 2 -N 3，O（2B）氨基氧代和κ 2 -N 3，N4（2C）亚氨基氧代互变异构体。主要异构体2B联营公司与未成年一个2C通过N·H···N和N·H···O的氢键形成[ 2b · 2c ] 2二聚体，它们从2的饱和戊烷溶液中结晶。配合物1还能够对胞嘧啶（cytosinate'）进行双去质子化反应，得到双核衍生物（P i Pr 3）2 H 3 Os（cytosinate'）OsH 3（P i Pr 3）2（3），其中阴离子配位κ 2 -N1，O和κ 2 -N 3，N4到两个不同的职业安全与卫生3（P我镨3）2个金属碎片。脱氧胞苷和胞苷导致职业安全与卫生去质子化3（deoxyc
• Osmium-Promoted Transformation of Alkyl Nitriles to Secondary Aliphatic Amines: Scope and Mechanism
  作者：Juan C. Babón、Miguel A. Esteruelas、Ana M. López、Enrique Oñate

  DOI：10.1021/acs.organomet.0c00236

  日期：2020.6.8

  symmetrical and asymmetrical secondary aliphatic amines promoted by the hexahydride complex OsH6(PiPr3)2 (1) is described, and the mechanisms of the reactions involved are established. Complex 1 catalyzes the aforementioned transformations of aryl-, pyridyl-, and alkoxy-functionalized alkyl nitriles with linear or branched chains. The formation of the secondary amines involves primary imines, primary amines

  描述了由六氢化物配合物OsH 6（P i Pr 3）2（1）促进的烷基腈向对称和不对称仲脂肪族仲胺的转化，并建立了涉及的反应机理。配合物1催化具有直链或支链的芳基，吡啶基和烷氧基官能化的烷基腈的上述转化。仲胺的形成涉及伯亚胺，伯胺和仲亚胺作为有机中间体。反应在温和的条件下（甲苯，100°C和4 bar H 2）进行。1的化学计量反应与新戊腈和2-甲氧基乙腈一起使我们能够分离三氢化物氮杂亚乙烯基衍生物OsH 3 ═N═CHR}（P i Pr 3）2（R = t Bu（3），CH 2 OMe（4））。它们的形成涉及将底物的N–C三键插入不饱和四氢化物OsH 4（P i Pr 3）2（A）的Os–H键中，这是通过从六氢化合物中消除H 2产生的前体。这些三氢化物氮杂亚乙烯基物质与H 2的反应是还原腈的N-C三键的关键步骤。在没有H 2的情况下，A对氮杂亚乙烯基配体的攻击会导致其C（sp 2）–C（sp