heptahydrido bis(tricyclohexylphosphine)rheniume(VII) | 92284-90-7

• 分子结构分类: 有机化合物
• 英文名称: heptahydrido bis(tricyclohexylphosphine)rheniume(VII)
• 英文别名: rhenium bis tricyclohexylphosphine heptahydride；ReH₇(tricyclohexylphosphine)₂；ReH₇(PCy₃)₂；ReH7(PCy3)2；rhenium heptahydride;tricyclohexylphosphane
• CAS: 92284-90-7
• 化学式: C₃₆H₇₃P₂Re
• 分子量: 754.13
• InChiKey: MAIBZXFLXFFJKV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.06
• 重原子数：
  39.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• 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：

  heptahydrido bis(tricyclohexylphosphine)rheniume(VII) 在 三苯基膦 作用下， 以 甲苯 为溶剂， 生成 bis(tricyclohexyl-l5-phosphaneyl)(triphenyl-l5-phosphaneyl)rhenium(VIII) hydride
  参考文献：
  名称：

  铼配合物ReH7[P(C6H11)3]2活化碳氢键的机理特征

  摘要：

  Dans l'intervalle 60-80°C, le complexe du titre echange l'hydrogene avec le deuteriobenzo。Le deuterium est incorpore dans le complexe non seulement ent que coordinats hydruro mais aussi selection sur les carbones C 2 et C 3 de tous les cycle cyclohexyles。D'apres l'observation de l'echange avec D 2 et les etudes cinetiques de la reaction du complexe du titre avec des phosphines et nucleophiles eneiques

  DOI：

  10.1021/ja00335a024
• 作为产物：
  描述：

  ReOCl₃(tricyclohexylphosphine)₂ 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 以70%的产率得到heptahydrido bis(tricyclohexylphosphine)rheniume(VII)
  参考文献：
  名称：

  铼配合物ReH7[P(C6H11)3]2活化碳氢键的机理特征

  摘要：

  Dans l'intervalle 60-80°C, le complexe du titre echange l'hydrogene avec le deuteriobenzo。Le deuterium est incorpore dans le complexe non seulement ent que coordinats hydruro mais aussi selection sur les carbones C 2 et C 3 de tous les cycle cyclohexyles。D'apres l'observation de l'echange avec D 2 et les etudes cinetiques de la reaction du complexe du titre avec des phosphines et nucleophiles eneiques

  DOI：

  10.1021/ja00335a024
• 作为试剂：
  描述：

  3,4-二氢-1(2H)-萘酮 、 4-甲氧基苄醇 在 heptahydrido bis(tricyclohexylphosphine)rheniume(VII) 、 lithium chloride 作用下， 以63%的产率得到(E)-2-(4-methoxybenzylidene)-3,4-dihydro-2H-naphthalen-1-one
  参考文献：
  名称：

  Rhenium-Catalyzed Acceptorless Dehydrogenative Coupling via Dual Activation of Alcohols and Carbonyl Compounds

  摘要：

  The rhenium hetaphydride complex was found to be a versatile, homogeneous catalyst for dehydrogenative functionalization of alcohol. The dehydrogenative C-C coupling of alcohols and carbonyl compounds was carried out in the absence Of base and hydrogen acceptors to afford a series of alpha,beta-unsaturated carbonyl compounds. A possible dual activation pathway was proposed by mechanistic investigations.

  DOI：

  10.1021/cs400572q

文献信息

• The reversible protonation of rhenium(<scp>VII</scp>) heptahydrides of type [ReH₇(PR₃)₂] to give η²-dihydrogen complexes
  作者：Xavier L. R. Fontaine、Edmund H. Fowles、Bernard L. Shaw

  DOI：10.1039/c39880000482

  日期：——

  The first examples of the protonation of d0 metal complexes of type [ReH7(PR3)2][PR3= P(cyclohexyl)3, PPh3 or PBut2Me], to give η2-H2 complexes, are described.

  描述了d0金属配合物[ReH7(PR3)2]（其中PR3为P(cyclohexyl)3、PPh3或PBut2Me）质子化的首个实例，以形成η2-H2配合物。
• Intra- and inter-ion-pair protonic-hydridic bonding in polyhydridobis(phosphine)rhenates
  作者：Kamaluddin Abdur-Rashid、Alan J Lough、Robert H Morris

  DOI：10.1139/v01-071

  日期：2001.5.1

  The hexahydridobis(phosphine)rhenate anions, [ReH6(PR3)2]- (PR3 = PCy3, P-i-Pr3, PPh3, PMe3) were generated by potassium hydride deprotonation of the neutral heptahydride conjugate acids (ReH7(PR3)2), isolated as their [K(18-crown-6)]+ and [K(1,10-diaza-18-crown-6)]+ salts, and characterized by NMR and IR spectroscopy and elemental analyses. Structures from single crystal X-ray diffraction were obtained

  六氢化双（膦）铼酸阴离子 [ReH6(PR3)2]- (PR3 = PCy3, Pi-Pr3, PPh3, PMe3) 是通过中性七氢化物共轭酸 (ReH7(PR3)2) 的氢化钾去质子化生成的，分离作为它们的 [K(18-crown-6)]+ 和 [K(1,10-diaza-18-crown-6)]+ 盐，并通过核磁共振和红外光谱以及元素分析进行​​表征。[K(1,10-diaza-18-crown-6)]+盐的单晶 X 射线衍射结构表明存在涉及阴离子氢化物和阳离子的质子供体NH部分。[K(1,10-diaza-18-crown-6)][ReH6(Pi-Pr3)2]的结构采用一维锯齿链，阳离子和阴离子交替连接并通过离子间NH·保持在一起··Hx-Re 相互作用（x = 1 或 2）。对于该复合物，估计阳离子的 NH 质子和阴离子的氢化物之间的短距离范围为 1.6 至 1.9 A。[K(1
• Rhenium-catalyzed amination of alcohols by hydrogen transfer process
  作者：Ablimit Abdukader、Hongming Jin、Yixiang Cheng、Chengjian Zhu

  DOI：10.1016/j.tetlet.2014.05.068

  日期：2014.7

  The rhenium heptahydride complex [ReH7(PCy3)2] was found to be an effective homogeneous catalyst for amination of various alcohols through hydrogen transfer mechanism. Under carbon monoxide atmosphere, a variety of primary and secondary alcohols could directly undergo the CN coupling process.

  发现七氢化rh络合物[ReH 7（PCy 3）2 ]是通过氢转移机理胺化各种醇的有效均相催化剂。在一氧化碳气氛下，各种伯醇和仲醇可以直接经历C N偶联过程。
• Properties of the Polyhydride Anions [WH₅(PMe₂Ph)₃]^- and [ReH₄(PMePh₂)₃]^- and Periodic Trends in the Acidity of Polyhydride Complexes
  作者：Justin G. Hinman、Alan J. Lough、Robert H. Morris

  DOI：10.1021/ic062037b

  日期：2007.5.1

  X-ray diffraction study of the crypt salt. No hydridic-protonic M-H...HN bonding is detected between the hydrides of the anionic hydrides and the amino hydrogens of the cations [K(1,10-diaza-18-crown-6)]+ suggesting that stronger M-H...K interactions are present. Acid dissociation constants Ka of polyhydride complexes in THF, approximately corrected for ion pairing, are determined by NMR in order to better

  新的阴离子络合物[K（18-crown-6）] [WH5（PMe2Ph）3]，[K（1,10-diaza-18-crown-6）] [WH5（PMe2Ph）3]，[K（2 ，2,2-crypt）] [ReH4（PMePh2）3]和[K（1,10-diaza-18-crown-6）] [ReH4（PMePh2）3]是通过KH / crown或KH反应制备的/ crypt使用适当的中性多羟基化合物WH6（PMe2Ph）3或ReH5（PMePh2）3。与冠状反应相比，涉及隐窝反应的氢化rh在THF中的去质子速率要大得多。通过隐窝盐的X射线衍射研究确定，[ReH4（PMePh2）3]-的结构是扭曲的五边形双锥体。在阴离子氢化物的氢化物和阳离子[K（1,10-diaza-18-crown-6）] +的氨基氢之间未检测到氢-质子化的MH ... HN键，表明更强的MH ...存在K相互作用。THF中多
• Rhenium Dihydrogen Complexes with Isonitrile Coligands:  Novel Displacement of Chloride by Hydrogen
  作者：D. M. Heinekey、Mark H. Voges、David M. Barnhart

  DOI：10.1021/ja961994p

  日期：1996.1.1

  The syntheses, properties, and characterization of several new complexes, Re(CNtBu)(3)(PCy(3))(2)H (1a), Re(CNtBu)(3)(PR(3))(2)Cl [R = Cy, Ph (2a, 2b)], the 17-electron [Re(CNtBu)(3)(PCy(3))(2)Cl](+) (3a), the dihydrogen complex, [Re(CNtBu)(3)(PR(3))(2)(H-2)](+) [R = Cy, Ph (4a, 4b)], the coordinatively unsaturated [Re(CNtBu)(3)(PCy(3))(2)](+) (5a), and [Re(CNtBu)(4)(PCy(3))(2)](+) (6a) are reported. In addition, spectroscopic evidence for the dinitrogen complex [Re(CNtBu)(3)-(PCy(3))(2)(N-2)](+), and the dihydrogen complex [Re(CNtBu)(5)(H-2)](+) is presented. Thermodynamic parameters have been obtained for the equilibrium system, Re(CNtBu)(3)(PCy(3))(2)Cl (2a) + H-2 reversible arrow [Re(CNtBu)(3)(PCy(3))(2)(H-2)]Cl (4a). H-1 and P-31H-1} NMR studies (CD2Cl2) over the temperature range 286-316 K afford values of Delta H degrees = -18.0 +/- 0.7 kcal/mol, Delta S degrees = -44 +/- 2 eu, and Delta G degrees(298) = -4.8 +/- 1.3 kcal/mol for this equilibrium. The complexes 4a and 4b are characterized as dihydrogen complexes. Their J(HD) (R = Cy, 30.3 Hz; R = Ph, 30.9 Hz) and T-l(min) values of 8 ms (300 MHz) are consistent with H-H distances of ca. 0.80 Angstrom. [Re(CNtBu)(5)(HD)](+) is also characterized as a dihydrogen complex based on a J(HD) of 33.4 Hz. This complex could not be isolated at room temperature, even with noncoordinating counteranions, due to the lability of the H-2 ligand. [Re(PMe(3))(5)HD](+) shows no H-D coupling and is characterized as a dihydride complex. The unsaturated complex [Re(CNtBu)(3)(PCy(3))(2)](+) (5a) is found to undergo a dynamic isonitrile rearrangement on the NMR time scale. H-1 NMR spin saturation transfer studies over a temperature range of 254-297 K afford the activation parameters Delta H double dagger = 11.4 +/- 0.8 kcal/mol, Delta S double dagger = -17.6 +/- 1.6 eu, and Delta G double dagger(298) = 16.6 +/- 1.2 kcal/mol. The molecular structures of 2a and 3a have been determined by X-ray crystallography. 2a shows an unusually long Re-Cl bond distance of 2.596(2) Angstrom.