bis(triisopropylphosphane)(dihydrido)dichloroosmium(IV) | 131296-70-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: bis(triisopropylphosphane)(dihydrido)dichloroosmium(IV)
• 英文别名: Os(H)2Cl2(P(i)Pr3)2；dichloro(dihydrido)osmium;tri(propan-2-yl)phosphane
• CAS: 131296-70-3
• 化学式: C₁₈H₄₄Cl₂OsP₂
• 分子量: 583.601
• InChiKey: GXENNLVKGJRDAC-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.23
• 重原子数：
  23.0
• 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：

  bis(triisopropylphosphane)(dihydrido)dichloroosmium(IV) 在 (C₂H₅)3N 作用下， 生成 (2,2,2-trifluoroethoxy)bis(triisopropyl-l5-phosphaneyl)osmium(VI) hydride
  参考文献：
  名称：

  Quantum Exchange Coupling:  A Hypersensitive Indicator of Weak Interactions

  摘要：

  Os(H)(3)ClL2 (L = (PPr3)-Pr-i) forms a 1:1 adduct with L' = PEt3, NH3, MeCN, acetone, methanol, and THF. The case L' = PEt3 permits the dearest identification of adduct structure as pentagonal bipyramidal. For NH3 and MeCN, the respective kinetics of L' loss are measured as Delta H-double dagger = 20.7(3) and 17.6(3) kcal/mol and Delta S-double dagger = 16(1) and 14.7(9) cal/(mol K). For acetone, methanol, and THF, the following respective Delta H degrees and Delta S degrees values for L' binding are measured: Delta H degrees = -10.4(1), -6.66(8), and -5.8(2) kcal/mol; Delta S degrees = -41.8(5), -25.5(3), and -33(1) cal/(mol K). Decoalesced H-1 NMR spectra are reported for several of these Os(H)(3)ClL2L' species, and they show a variety of examples of quantum exchange coupling among the hydride ligands. The values of J(e)x are higher when L' is a more weakly-binding ligand. The quantum exchange coupling constants of Os(H)(3)XL2 (X = Cl, Br, I, OCH2CF3, OCH(CF3)(2)) in CD2Cl2, in toluene, and in methylcyclohexane show an unprecedented decrease of J with increasing temperature, which is attributed to weak formation of Os(H)(3)Cl(solvent)L-2 adducts at low temperature. For L' = CO, adduct formation leads to liberation of coordinated H-2. Excess L' = MeCN or NH3 slowly leads to formation of [Os(H)(3)L'L-2(2)]Cl; the X-ray structure for L' = NH3 is reported. Crystal data (-171 degrees C): a = 11.561(4) Angstrom, b = 14.215(5) Angstrom, c = 8.851(3) Angstrom, alpha = 97.51(2)degrees, beta = 107.73(2)degrees, gamma = 104.47(2)degrees, with Z = 2 in space group . The potential energy was calculated for exchange of 2H of OsH3X(PH3)(2)L (X = Cl with L = no ligand and PH3, X = I with L = no ligand) using effective core potential ab initio methods at the MP2 level. The site exchange is found to be energetically easier for Cl than for I, in agreement with experiment. The hydride site exchange in the seven-coordinate species OsH3Cl(PH3)(3) (a model for coordination of either ligand or solvent to Os) is found to be easier than that in the 16-electron species. No dihydrogen ligand is located on the reaction path for site exchange. The current theory which relates quantum exchange to a tunneling effect was used for calculating J(ex) as a function of temperature. The dynamic study was done using several sets of coordinates, in particular the rotation angle phi and the internuclear distance r between the exchanging H. The vibrational levels have been calculated and the symmetry of each level assigned within the permutation group in order to determine the nature of the nuclear spin function associated with each level. It is found that the rotation, phi, gives rise to the largest tunneling effect but that r cannot be neglected. The influence of the temperature, J(ex)(T), was included by a Boltzmann distribution. The results are in qualitative agreement with experiment in that quantum exchange coupling is larger in the case of Cl than in the case of I. Additional ligand L increases the value of the quantum exchange coupling mostly by lowering the activation energy for pairwise exchange.

  DOI：

  10.1021/ja970603j
• 作为产物：
  描述：

  trans,trans-OsCl2(η2-H2)(acetonitrile)(P(i)Pr3)2 以 氘代苯 为溶剂， 生成 bis(triisopropylphosphane)(dihydrido)dichloroosmium(IV)
  参考文献：
  名称：

  Behavior of OsH₂Cl₂(PⁱPr₃)₂ in Acetonitrile: The Importance of the Small Details

  摘要：

  The behavior of OsH2Cl2((PPr3)-Pr-i)(2) (1) in acetonitrile as solvent is studied. Acetonitrile coordinates to the metal center of 1 and promotes the dihydride-dihydrogen transformation of its OsH2 unit to give the trans-Cl-2 compound OsCl2(eta(2)-H-2)(CH3CN)((PPr3)-Pr-i)(2) (2a), which evolves to its cis-Cl-2 isomer 2b. Treatment of 1 with TlPF6 in acetonitrile leads to the PF6 salt of the cis-bis(acetonitrile) cation [OsCl(eta(2)-H-2)(CH3CN)(2)((PPr3)-Pr-i)(2)](+) (3a), which is transformed into its trans-bis(acetonitrile) isomer 3b. The addition of Et3N to the PF6 salts of 3a,b in acetonitrile gives [OsH(CH3CN)(3)((PPr3)-Pr-i)(2)]PF6 (4). Reaction of 4 with 1,5-cyclooctadiene (COD) in refluxing toluene affords [OsH(COD)(CH3CN)(2)((PPr3)-Pr-i)]PF6 (5). The X-ray structures of 3b and 5 are also reported.

  DOI：

  10.1021/om801057z
• 作为试剂：
  描述：

  dimethyl 2-((2E,4E)-hexa-2,4-dien-1-yl)-2-(buta-2,3-dien-1-yl)malonate 在 bis(triisopropylphosphane)(dihydrido)dichloroosmium(IV) 、 甲醇 作用下， 以 甲苯 为溶剂， 反应 1.0h， 生成 dimethyl 2-(but-3-en-1-yl)-2-((2E,4E)-hexa-2,4-dien-1-yl)malonate 、 dimethyl 2-((Z)-but-2-en-1-yl)-2-((2E,4E)-hexa-2,4-dien-1-yl)malonate
  参考文献：
  名称：

  All（IV）配合物与烯丙二烯的反应：配位和分子内环加成反应

  摘要：

  OsH 2 Cl 2（P i Pr 3）2（1）与二甲基（E）-2-（buta-2,3-dien-1-yl）-2-（penta-2,4-dien- 1-基）丙二酸酯（I），2-（（2 E，4 E）-己二，4-二烯-1-基）-2-（丁二，3-二烯-1-基）丙二酸二甲酯（II）和二（E）-2-（戊-2,3-二烯-1-基）-2-（戊-2,4-二烯-1-基）丙二酸二甲酯（III）已被研究。与I的反应得到OsCl 2（P i Pr 3）2（烯丙二烯）与有机配体的复合物，该有机配体由烯丙基部分的末端双键配位。在353ķ甲苯，该化合物演变成一个（η 6 -arene）OSCL 2（P我镨3）2种。芳烃配体是由配位的烯丙二烯分子的分子内（4 + 2）环加成和随后的芳构化以及氢损失造成的四氢茚的芳构化而产生的。1与II的反应生成的烯丙二烯络合物与I相似。然而，在这种情况下，烯丙二烯物种演变成氢化卡宾炔衍生物。综合大楼1促进III的（2

  DOI：

  10.1021/om300236y

文献信息

• Hydride Alkenylcarbyne Osmium Complexes versus Cyclopentadienyl Type Half-Sandwich Ruthenium Derivatives
  作者：Alba Collado、Miguel A. Esteruelas、Enrique Oñate

  DOI：10.1021/om1011962

  日期：2011.4.11

  2-methyl-1-hexen-3-yne to give a complex mixture of compounds, from which the derivatives Ru(η5-C5HR1R2R3R4)Cl(PiPr3) (17; R1 = C(CH3)═CH2, R2 = Et, R3 = nPr, R4 = Me) and RuCl2═C(Et)CH═CMe2}(PiPr3)2 (18, traces) are isolated. Both 17 and 18 have been also characterized by X-ray diffraction analysis. DFT calculations (B3PW91) on the formation of 17 suggest that in the ruthenium case the hydrogenation of

  二氢化物络合物OsH 2 Cl 2（P i Pr 3）2（1）与2-甲基-1-己烯-3-炔和2,4-二甲基-1,3-戊二烯反应，得到氢化物烯基碳炔衍生物OsHCl 2 ≡CC（Me）═CHR}（P i Pr 3）2（R = n Pr（2），i Pr（3）），已通过X射线衍射分析对其进行了表征。DFT计算（B3PW91）表明，烯炔首先被氢化以提供共轭二烯。后者通过两个氢迁移而演变成氢化物链烯基碳炔衍生物。第一个迁移是二烯中的1，4-氢转移（从末端CH 2基团到内部双键），该转移通过金属中心发生。第二个迁移是从末端CH 2基团到the原子的1,2-氢转移。与1的情况相反，钌的对应物RuH 2 Cl 2（P i Pr 3）2（16）与2-甲基-1-己烯-3-炔反应，得到的化合物的复杂混合物，从该衍生物的Ru（η 5 -C 5 HR 1 - [R 2 - [R 3 - [R 4）氯（P我镨3）（17
• 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％
• 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）。
• Meyer's Complex OsH₂Cl₂(PⁱPr₃)₂ as a Precursor for the Preparation of New Cyclopentadienylosmium Compounds
  作者：Miguel A. Esteruelas、Ana M. López、Natividad Ruiz、José I. Tolosa

  DOI：10.1021/om970237c

  日期：1997.10.1

  OsH(η5-C5H5)(PiPr3)2 (4) , which by protonation with HBF4·OEt2 yields [OsH2(η5-C5H5)(PiPr3)2]BF4 (5). In pentane, complex 2 reacts with trimethyl phosphite to give Os(η5-C5H5)ClP(OMe)3}(PiPr3) (6). Similarly, the addition of methyl vinyl ketone and dimethyl acetylenedicarboxylate to toluene solutions of 2 produces the displacement of a phosphine ligand from 2 and the formation of Os(η5-C5H5)Clη2-CH2CHC(O)CH3}(PiPr3)

  的六配位配合物OSH 2氯2（P我镨3）2（1）反应以cyclopentadienylthallium给OS（η 5 -C 5 H ^ 5）氯（P我镨3）2（2）。在甲醇和丙酮中，2使氯配体解离，得到的金属片段能够活化三异丙基膦的甲基CH键，可以通过添加NaPF 6或TlPF 6将其分离为PF 6盐。。的1:10混合物的治疗2和NaBH 4在甲苯用1.0毫升甲醇，得到OSH（η的5 -C 5 H ^ 5）（P我镨3）2（4），其通过与HBF质子化4 ·OET 2产率[OSH 2（η 5 -C 5 H ^ 5）（P我镨3）2 ] BF 4（5）。在戊烷中，复杂的2种发生反应与亚磷酸三甲酯，得到OS（η 5 -C 5H 5）Cl P（OMe）3 }（P i Pr 3）（6）。类似地，除了甲苯溶液甲基乙烯基酮和乙炔二的2产生一个膦配位体从位移2和OS的形成（η 5 -C 5 H ^ 5）氯η
• C−H Bond Activation of Terminal Allenes: Formation of Hydride-Alkenylcarbyne-Osmium and Disubstituted Vinylidene-Ruthenium Derivatives
  作者：Alba Collado、Miguel A. Esteruelas、Fernando López、José L. Mascareñas、Enrique Oñate、Beatriz Trillo

  DOI：10.1021/om100192t

  日期：2010.11.8

  (M = Os (1), Ru (2)) toward allenes has been studied. Complex 1 reacts with 2 equiv of 3-methyl-1,2-butadiene and 1-methyl-1-(trimethylsilyl)allene to give 1 equiv of olefin and the π-allene derivatives OsCl2(η2-CH2═C═CRMe)(PiPr3)2 (R = Me (3), Me3Si (4)). The X-ray structure of 4 proves the coordination to the metal center of the carbon−carbon double bond of the allene with the lowest steric hindrance

  已经研究了二氢化物MH 2 Cl 2（P i Pr 3）2（M = OS（1），Ru（2））对丙二烯的反应性。复杂1种发生反应与2当量3-甲基-1,2-丁二烯和1-甲基-1-（三甲基硅烷基）丙二烯的反应，得到1-烯烃和π -丙二烯衍生物的当量OSCL 2（η 2 -CH 2 ═C═ CRMe）（P i Pr 3）2（R = Me（3），Me 3 Si（4））。X射线结构图4证明了位阻最低的丙二烯碳-碳双键与金属中心的配位。在甲苯中，配合物3和4不稳定，并演变成氢化物-烯基碳炔衍生物OSHCl 2（≡CCH═CRMe）（P i Pr 3）2（R = Me（5），Me 3 Si（6））。在模型化合物OSCL DFT计算2（η 2 -CH 2 ═C═CMe 2）（PME 3）2（3吨）表明π-丙二烯至氢化物-烯基碳炔的转化涉及丙二烯的CH 2基团的两个氢原子的迁移。它们中的第一个发生在末端碳原子