tetraphenylphosphonium cis-dihydridotetracarbonylrhenate | 118831-28-0

• 英文名称: tetraphenylphosphonium cis-dihydridotetracarbonylrhenate
• CAS: 118831-28-0
• 化学式: C₄H₂O₄Re*C₂₄H₂₀P
• 分子量: 639.661
• InChiKey: RYRAPHGVVLMRBM-UHFFFAOYSA-N

计算性质

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

• 作为反应物：
  描述：

  Re2(μ-H)2(CO)8 、 tetraphenylphosphonium cis-dihydridotetracarbonylrhenate 以 tetrahydrofuran-d8 为溶剂， 生成 [PPh4][Re3H2(μ-H)2(CO)12]
  参考文献：
  名称：

  New chain clusters of rhenium connected by Re–H–Re interactions: A low-temperature NMR investigation

  摘要：

  Low temperature NMR spectroscopy has been used to characterize the mixtures formed in the oligomerization reactions of the unsaturated complex [Re-2(mu-H)(2)(CO)(8)] (1), promoted by hydrido-carbonyl rhenates. Three families of chain clusters, constituted by Re(CO)(4) units connected through Re(mu-H)Re interactions, have been obtained. The first one, of general formula [(CO)(5)Re-{HRe(CO)(4)}(2n+1)], was formed using [HRe2(CO)(9)] as promoter. The nature of the products was confirmed by C-13 NMR of (CO)-C-13 enriched samples. The formation of Re-6 and Re-8 chain clusters was recognized. The other two families have general formula [H-{HRe(CO)(4)}(2n)] and [H-{HRe(CO)(4)}(2n+1)] and were obtained using as initiators [HB(Bu-s)(3)] or [H2Re(CO)(4)], respectively. Mixtures of oligomers with mean chain lengths higher than 10 have been observed. The addition of a strong acid caused H-2 evolution, leading back to the "monomer" 1. For all the three families, each oligomerization step was reversible, with the longer oligomers favoured at the lowest temperatures, where, however, the reactions were very slow, usually preventing the attainment of the equilibrium. Variable temperature NMR spectra revealed a dynamic process involving the terminal H2Re(CO)(4) moiety(ies), that simultaneously exchanges terminal/bridging hydrides and the carbonyls trans to them (Delta G(#) 41-44 kJ mol (1)). At room temperature, the more hydrogen-rich chain clusters also underwent dehydrogenation/cyclization reactions. (C) 2009 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2009.05.005
• 作为产物：
  描述：

  trisodium tetracarbonylrhenate(3-) 、 四苯基氯化膦 在 水 作用下， 以 六甲基磷酰三胺 、 水 为溶剂， 以85%的产率得到tetraphenylphosphonium cis-dihydridotetracarbonylrhenate
  参考文献：
  名称：

  Highly reduced organometallics. Part 25. Reactions of trisodium tetracarbonylmetalates(3-) of manganese and rhenium with Broensted acids and other electrophiles. Synthesis of H2M(CO)4- (M = Mn and Re), (CH3)2Re(CO)4-, the first dialkyl derivative of a carbonylmetalate trianion, and related anionic species

  摘要：

  DOI：

  10.1021/ja00188a029

文献信息

• Reactivity patterns of the unsaturated tetrahedral cluster [Re₄(µ₃-H)₄(CO)₁₂]. Easy addition of four MeCN molecules and ‘ionic’ or ‘neutral’ fragmentation pathways of the spiked-triangle intermediate [Re₄(µ-H)₄(CO)₁₂(NCMe)₄]
  作者：Tiziana Beringhelli、Giuseppe D'Alfonso、Marta Zarini

  DOI：10.1039/dt9950002407

  日期：——

  The unsaturated (56 valence electrons, v.e.s) tetrahedral cluster [Re-4(mu(3)-H)(4)(CO)(12)] 1 readily added four acetonitrile molecules, affording two isomers 2a and 2b of the 64 v.e.s [Re-4(mu-H)(4)(CO)12- (NCMe)(4)] derivative, containing a spiked-triangle metallic skeleton. These isomers at room temperature rapidly underwent an ionic fragmentation to the known unsaturated triangular cluster anion [Re-3(mu-H)(4)(CO)(9)(NCMe)](-) and to the cation [Re(CO)(3)(NCMe)(3)](+). The rate of decomposition significantly increased at low [MeCN] concentration. Treatment of compounds 2a and 2b with the pi-acidic ligand CO, in the absence of free acetonitrile, gave only neutral products. Monitoring by NMR spectroscopy has revealed the rapid stepwise substitution of the nitrile ligands, accompanied by fragmentation to the known saturated triangular clusters [Re-3(mu-H)(3)(CO)(12-n)(NCMe)(n)] (n = 1-3) and to the mononuclear complexes [ReH(CO)(5-n)(NCMe)(n)] (n = 0 or 1). The novel, unstable. mononuclear hydride [ReH(CO)(4)(NCMe)] has been obtained by treatment of [ReH(CO)(5)] with Me(3)NO in acetonitrile and by reaction of [ReH2(CO)(4)](-) with CF3SO3H. in acetonitrile. In the presence of free acetonitrile, compounds 2a and 2b reacted with CO more slowly and gave both anionic and neutral triangular clusters.
• [Re5(μ-H)4(CO)20]− and [Re5(μ-H)5(CO)20], Two Isolobal Analogues of Cyclopentane
  作者：Mirka Bergamo、Tiziana Beringhelli、Giuseppe D'Alfonso、Pierluigi Mercandelli、Massimo Moret、Angelo Sironi

  DOI：10.1002/(sici)1521-3773(19980817)37:15<2128::aid-anie2128>3.0.co;2-7

  日期：1998.8.17

  The first five-membered rings of metal atoms connected by M-M or M-H-M bonds only have been obtained by a Re2 +Re3 condensation in which a polyhydride acts as a bridging bidentate ligand toward a coordinatively unsaturated fragment (see scheme below). In spite of the octahedral coordination of the Re centers, the Re5 rings display conformations (twisted and envelope) comparable with those observed for organic five-membered rings of tetrahedral carbon atoms.