(η5-C5H5)Re(NO)(PPh3)(CCH) | 82582-43-2

• 英文名称: (η5-C5H5)Re(NO)(PPh3)(CCH)
• CAS: 82582-43-2
• 化学式: C₂₅H₂₁NOPRe
• 分子量: 568.629
• InChiKey: SZCFYWOCDKJAFI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (η5-C5H5)Re(NO)(PPh3)(CCH) 在 正丁基锂 、 碘甲烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以91%的产率得到(η5-C5H4CH3)Re(NO)(PPh3)(CCHCH3)
  参考文献：
  名称：

  Reactions of the terminal rhenium acetylide complex Re(η⁵-C₅H₅)(NO)(PPh₃)(CCH) and butyllithium; generation, alkylation and stannylation of lithiocarbide complexes of the formula Re(η⁵-C₅H₄)(NO)(PPh₃)(CCLi)(X = H, Li)

  摘要：

  该标题反应根据反应计量和条件生成Re(η⁵-C₅H₅)(NO)(PPh₃)(CCLi)和Re(η⁵-C₅H₄Li)(NO)(PPh₃)(CCLi)；这是首次制备的过渡金属-碱金属碳化物复合物，随后通过碳和金属电亲体进行衍生化。

  DOI：

  10.1039/c39910001360
• 作为产物：
  描述：

  {(η5-C5H5)Re(NO)(PPh3)(HCCH)}BF4 在 (CH₃)3COK 作用下， 以 四氢呋喃 为溶剂， 以74%的产率得到(η5-C5H5)Re(NO)(PPh3)(CCH)
  参考文献：
  名称：

  Kowalczyk, James J.; Arif, Atta M.; Gladysz, Organometallics, 1991, vol. 10, # 4, p. 1079 - 1088

  摘要：

  DOI：

文献信息

• Synthesis, structure, and reactions of chiral rhenium vinylidene and acetylide complexes of the formula [(.eta.5-C5H5)Re(NO)(PPh3)(X)]n+. Vinylidene complexes that are formed by stereospecific C.beta. electrophilic attack, exist as two Re=C=C geometric isomers, and undergo stereospecific C.alpha. nucleophilic attack
  作者：Dwayne R. Senn、Andrew. Wong、Alan T. Patton、Marianne. Marsi、Charles E. Strouse、J. A. Gladysz

  DOI：10.1021/ja00226a026

  日期：1988.8

  (a) high-yield syntheses of chiral rhenium vinylidene complexes ((/eta//sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(/emdash/C/emdash/CRR/prime/))/sup +/X/sup /minus// and acetylide complexes (/eta//sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(C/identical to/CR), (b) the first observation of M/emdash/C/emdash/C geometric isomerism in vinylidene complexes, (c) the thermal and photochemical interconversion

  在本文中，作者报告了 (a) 手性亚乙烯基铼配合物 ((/eta//sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/ )(/emdash/C/emdash/CRR/prime/))/sup +/X/sup /minus// 和乙炔化合物 (/eta//sup 5/-C/sub 5/H/sub 5/)Re (NO)(PPh/sub 3/)(C/identical to/CR), (b) M/emdash/C/emdash/C 在亚乙烯基配合物中的几何异构现象的首次观察，(c) 热和光化学互变这些几何异构体和相应的速率和活化参数，（d）立体有择的 C/sub /alpha// 对亚乙烯基配合物的亲核攻击和立体有择的 C/sub /beta// 对乙炔配合物的亲电攻击的例子，以及（e） X 射线晶体结构建立了两种类型复合物的这些转换和键合特征的立体化学。这项研究的一部分已被传达。
• Syntheses and reactions of rhenium vinylidene and acetylide complexes. Unprecedented chirality transfer through a C.tplbond.C triple bond
  作者：Andrew Wong、J. A. Gladysz

  DOI：10.1021/ja00382a036

  日期：1982.9

  and acetylide complexes ((eta-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(==C identical with CRR'))/sup +/X/sup -/ (1) and (eta-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(C identical with CR) (2) R,R' = H, CH/sub 3/, C/sub 6/H/sub 5/), (b) unique observation of geometric isomerism in vinylidene complexes, (c) the thermal and photochemical interconversion of these isomers, (d) energy barriers associated with these

  我们描述了 (a) 手性亚乙烯基铼和乙炔配合物 ((eta-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(==C 与 CRR' 相同) 的简便合成))/sup +/X/sup -/ (1) 和 (eta-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(C 与 CR 相同) (2) R ,R' = H, CH/sub 3/, C/sub 6/H/sub 5/), (b) 亚乙烯基配合物中几何异构现象的独特观察, (c) 这些异构体的热和光化学互变, (d ) 与这些异构化相关的能量势垒，以及 (e) 乙炔络合物 2 的立体特异性反应，该反应需要通过形式圆柱对称的 C==C 三键转移金属手性。
• Ramsden, James A.; Weng, Weiqing; Gladysz, Organometallics, 1992, vol. 11, # 11, p. 3635 - 3645
  作者：Ramsden, James A.、Weng, Weiqing、Gladysz

  DOI：——

  日期：——
• Toward Metal-Capped One-Dimensional Carbon Allotropes:  Wirelike C₆−C₂₀ Polyynediyl Chains That Span Two Redox-Active (η⁵-C₅Me₅)Re(NO)(PPh₃) Endgroups
  作者：Roman Dembinski、Tamás Bartik、Berit Bartik、Monika Jaeger、J. A. Gladysz

  DOI：10.1021/ja992747z

  日期：2000.2.1

  Reaction of the butadiynyl complex (eta(5)-C5Me5)Re(No)(PPh3)(C drop CC drop CH) (ReC4H) with Cu(OAc)(2) (pyridine, 80 degrees C) gives the mu-octatetraynediyl complex ReC8Re (70%). Analogous cross-coupling of ReC4H and ReC2H gives (after chromatography) ReC4Re (14%), ReC6Re (44%), and ReC8Re (15%). Longer sp carbon chains are accessed by reactions of ReC4H with n-BuLi and CuI, which give ReC4Cu. This isolable species is treated in situ with BrC drop CSiEt3 or BrC drop CC drop CSiMe3 (excess EtNH2, THF) to give ReC6SiEt3 or ReC8SiMe3 (84-77%). Desilylations (wet n-Bu4N+F-) yield ReC6H or ReC8H (88-73%). Then Cu(OAc)(2) (pyridine, 50 degrees C) gives ReC12Re or ReC16Re (71-67%). The former is also available from ReC4Cu and BrC drop CC drop CBr (45%), and ReC10Re can be accessed by cross-coupling. ReC6H and ReC8H are similarly converted to ReC10SiR3 (R = Me, Et; 51-26%) and ReC12SiMe3 (43%). Desilylation of ReC10SiR3 gives labile ReC10H, but only black powder is obtained from ReC12SiMe3. In situ coupling of ReC10H gives ReC20Re (52-34%), which unlike lower homologues is not obtained in analytically pure form. The effects of chain length upon visible spectra (progressively red-shifted and more intense bands; epsilon > 190 000 M-1 cm(-1)), IR/ Raman nu(C drop C) patterns (progressively more bands),C-13 NMR chemical shifts (asymptotic limit of 64-67 ppm for ReC drop C((C) under bar drop (C) under bar)(n)), cyclic voltammetry (decreased reversibility of two oxidations; a gradual shift of the first to thermodynamically less favorable potentials, so that only a single oxidation is observed for ReC20Re), and thermal stabilities (solid-state decompositions at 155 degrees C, ReC20Re, and 178-217 degrees C, lower homologues) are studied in detail.