hydridopentakis(trimethylphosphine)rhenium | 84756-10-5

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: hydridopentakis(trimethylphosphine)rhenium
• CAS: 84756-10-5
• 化学式: C₁₅H₄₆P₅Re
• 分子量: 567.606
• InChiKey: ZIGIXGZPPAUFKN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.52
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 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：

  hydridopentakis(trimethylphosphine)rhenium 在 hydrogen 作用下， 以 light petroleum 为溶剂， 以96%的产率得到trihydridotetrakis(trimethylphosphine)rhenium
  参考文献：
  名称：

  Transition metal–hydrogen–alkali metal bonds: synthesis and crystal structures of [K(18-crown-6)][W(PMe₃)₃H₅], [Na(15-crown-5)][W(PMe₃)₃H₅] and [{W(PMe₃)₃H₅Li}₄] and related studies

  摘要：

  The new compounds K[W(PMe3)H-3(5)], [K(18-crown-6)][W(PMe3)H-3(5)] (18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane), Na[W(PMe3)H-3(5)], [Na(15-crown-5)][W(PMe3)H-3(5)], (15-crown-5 = 1,4,7,10,13-pentaoxacyclopentadecane), [{W(PMe3)H-3(5)Li}4], K[W(eta-C5H5)(PMe3)H-4], [K(18-crown-6)][W(eta-C5H5)(PMe3)H-4], [K(18-crown-6)][W(eta-C5H4Et)(PMe3)H-4], K[cis-Re(PMe3)H-4(2)], [K(18-crown-6)][cis-Re(PMe3)H-4(2)], [W(PMe3(H-3(5)(SnBu(n)3)], [W(eta-C5H5)(PMe3)H-4(SnBu(n)3)], [Re(PMe3)H-4(2)(SnBu(n)3)], [H(eta-C5H5)2ZrW(PMe3)H-3(5)], [Cl(eta-C5H5)2ZrW(PMe3)H-3(5), [{(Ph3P)Au}3W(PMe3)H-3(4)]Cl.xCH2Cl2 and [K(18-crown-6)][Mo(eta-C5H5)H-2] are reported. The X-ray crystal structures of [K(18-crown-6)][W(PMe3)H-3(5)], [Na(15-crown-5)][W(PMe3)H-3(5)], [{W(PMe3)3H5Li}4], [K(18-crown-6)][cis-Re(PMe3)H-4(2)], [{(Ph3P)Au}3W(PMe3)H-3(4)]Cl.0.15CH2Cl2 and [K(18-crown-6)][Mo(eta-C5H5)H-2] have been determined. The crystal structures of [K(18-crown-6)][W(PMe3)H-3(5)] and [Na(15-crown-5)][W(PMe3)H-3(5)] have also been determined by neutron diffraction. Evidence for the presence of a degree of covalent bonding in the systems M-H-M', where M = W and M' = Li, Na or K and M = Re, M' = K, is discussed.

  DOI：

  10.1039/dt9910002185
• 作为产物：
  描述：

  三甲基膦 、 rhenium(V) chloride 在 sodium 作用下， 以 neat (no solvent) 为溶剂， 以20%的产率得到hydridopentakis(trimethylphosphine)rhenium
  参考文献：
  名称：

  IV-VII 族过渡金属有机金属化学的新进展

  摘要：

  茂钨对碳-氢键的均相活化以及对茂钨衍生物中可逆 1,2-氢位移的观察导致对茂钨相关化学的研究不断扩大。描述了许多新化合物，它们被设计为茂钨前体类似物，并且已经探索了它们经历热或光化学诱导的 C-H 活化的能力。描述了简单的 d 钛-烷基，其中烷基配体的 C-H 基团形成共价的三中心双电子 Ti-H-C 键。首次描述了乙烷的活化。芳烃 - 亚烷基 - 铼衍生物形成并且似乎该反应对于许多烷烃和 sp 基团是通用的。

  DOI：

  10.1351/pac198456010047

文献信息

• Reactivity of nido-[2-{Fe(η-C₅H₅)}B₅H₁₀] with some transition-metal hydride complexes
  作者：H. Janet Bullick、Peter D. Grebenik、Malcolm L. H. Green、Andrew K. Hughes、John B. Leach、Philip Mountford

  DOI：10.1039/dt9940003337

  日期：——

  The reaction of nido-[2-Fe(eta-C5H5)}B5H10] with [Mo(PMe(2)Ph)(4)H-4] gave capped-closo-[1-Fe(eta-C5H5)}-2-Mo(PMe(2)Ph)(3)H}B5H7] which has been characterised by X-ray crystallography as well as by B-11 and H-1 NMR spectroscopy. The structure determination [monoclinic, space group P2(1)/c, a = 15.586(5), b=11.523(4). c=19.186(4) Angstrom, beta=106.23(2)degrees] reveals a capped-close geometry with one Fe-Mo-B face being capped by a boron atom and the other having a triply bridging hydrogen atom. The isostructural tungsten compound capped-closo-[1-Fe(eta-C5H5)}-2-W(PMe(3))(3)H}B5H7] was similarly prepared from [W(PMe(3))(3)H-6] and nido-[2-Fe(eta-C5H5)}B5H10]. Reaction between [Re(PMe(3))(5)H] and nido-[2-Fe(eta-C5H5)}B5H10] gave a mixture of nido-[2-Re(PMe(3))(3)}B(5)H10] and the salt [Re(PMe(3))(5)H-2](+) [nido-2-Fe(eta-C5H5)}B(5)H9(])(-), a product of an acid-base reaction.
• 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.
• Jones, William D.; Maguire, John A., Organometallics, 1987, vol. 6, # 8, p. 1728 - 1737
  作者：Jones, William D.、Maguire, John A.

  DOI：——

  日期：——
• Rosini, Glen P.; Jones, William D., Journal of the American Chemical Society, 1992, vol. 114, # 27, p. 10767 - 10775
  作者：Rosini, Glen P.、Jones, William D.

  DOI：——

  日期：——
• Allen, David L.; Green, Malcolm L. H.; Bandy, Judith A., Journal of the Chemical Society, Dalton Transactions
  作者：Allen, David L.、Green, Malcolm L. H.、Bandy, Judith A.

  DOI：——

  日期：——