(2,2'-bipyridine)ReOCl3 | 124509-53-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (2,2'-bipyridine)ReOCl3
• 英文别名: [Re(V)OCl3(bipyridine)]
• CAS: 124509-53-1
• 化学式: C₁₀H₈Cl₃N₂ORe
• 分子量: 464.752
• InChiKey: MSMGQFMAWANEEO-UHFFFAOYSA-K

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：

  (2,2'-bipyridine)ReOCl3 在 aniline 作用下， 以 邻二甲苯 为溶剂， 以65%的产率得到mer-PhNRe(2,2'-bipyridine)Cl3
  参考文献：
  名称：

  Synthesis and characterization of phenylimidorhenium(V) compounds containing polypyridyl ligands. Crystal structures of mer-[Re(NPh)Cl₃(bipy)], trans-[Re(NPh)(OEt)(bipy)₂][PF₆]₂and trans-[Re(NPh)Cl₂(terpy)]PF₆(bipy = 2,2′-bipyridine, terpy = 2,2′:6′,2″-terpyridine)

  摘要：

  The reaction between mer-[Re(O)Cl-3(L-L)] [L-L = 2,2'-bipyridine (bipy) or 4,4'-dimethyl-2,2'-bypyridine] and aniline in refluxing o-xylene gave phenylimido compounds formulated as mer-[Re(NPh)-Cl-3(L-L)]. These compounds do not react with an alcohol (ROH) to form alkoxyimido compounds of the type cis-[Re(NPh)(OR)Cl-2(L-L)], but in the presence of an excess of the polypyridyl ligand, salts of the cation trans-[Re(NPh)(OEt)(L-L)(2)](2+) were obtained. When salts of trans-[Re(NPh)(OEt)(L-L)(2)](2+) were dissolved in MeCN solutions containing a few drops of concentrated hydrochloric acid rapid reactions occurred that resulted in the isolation of mer-[Re(NPh)Cl-3(L-L)]. The salt trans-[Re(NPh)Cl-2(terpy)]PF6 was prepared from the reaction between mer-trans-[Re(NPh)-Cl-3(PPh(3))(2)] and 2,2':6'2 ''-terpyridine (terpy) in refluxing ethanol. The spectroscopic and electro-chemical properties of these compounds were investigated and the structures of mer-[Re(NPh)-Cl-3(bipy)], trans-[Re(NPh)(OEt)(bipy)(2)][PF6](2) and trans-[Re(NPh)Cl-2(terpy)]PF6 determined by x-ray crystallography.

  DOI：

  10.1039/dt9950001733
• 作为产物：
  描述：

  2,2'-联吡啶 、 [ReOCl3(OPPh3)(SMe2)] 以 四氢呋喃 为溶剂， 生成 (2,2'-bipyridine)ReOCl3
  参考文献：
  名称：

  包括吡啶基三嗪和吡嗪基三嗪在内的一系列联吡啶类配体的氧化铼 (V) 配合物：氧原子转移、金属氧化还原和相关性

  摘要：

  标题配体（通用缩写L）为联吡啶（bpy）、其二甲基（mbpy）和二苯基（pbpy）衍生物、菲咯啉（phen）、5,6-二苯基-3-（2-吡啶基）-1,2,4 -三嗪 (ppyt) 及其二甲基 (mpyt) 和吡嗪基 (ppzt) 类似物。相关的氧化配合物是[ReOCl3(L)]、[ReOBr3(ppyt)]和[ReOBr3(ppzt)]。ppyt 和 ppzt 的氯和溴配合物是通过这些配体与 [ReOX3(AsPh3)2] (X = Cl, Br) 反应制备的。[ReOCl3(ppyt)] 和 [ReOCl3(ppzt)] 的 X 射线结构表明 ReCl3 片段是经向排列的，L 配体是 N,N 配位的，因此吡啶/吡嗪氮与氧化氧原子。Re-O 长度 [1.656(10)/1.625(9) A] 对应于近似的三键。氧原子从溶液中的 [ReOX3(L)] 转移到三苯基膦的速率遵循二级动力学，并与大的负活化熵（约

  DOI：

  10.1002/ejic.200501102

文献信息

• Preparation and Characterization of Oxorhenium(V) Complexes with 2,2‘-Biimidazole:  The Strong Affinity of Coordinated Biimidazole for Chloride Ions via N−H···Cl^- Hydrogen Bonding
  作者：Sébastien Fortin、André L. Beauchamp

  DOI：10.1021/ic000328t

  日期：2000.10.1

  acetone (5% water) leads to the linear oxo-bridged dinuclear species [(OReCl2(biimMe2)2(mu-O)] containing chelated biimMe2. Acetone solutions containing only 1% water yield the bent oxo-bridged dinuclear species [(OReCl2)2(mu-O)(mu-biimMe2)2], where each Re center retains the ReO2Cl2N2 coordination but the biimMe2 ligands are bridging. The linear oxo-bridged [(OReCl2(biimH2)2(mu-O)] complex obtained

  N，N'-二甲基联咪唑和联吡啶（NN）与ReOCl3（OPPh3）（Me2S）反应生成mer-ReOCl3（NN）化合物。非甲基化的联咪唑形成反式-O，O [ReOCl2（OPPh3）（biimH2）] +阳离子，该阳离子通过NH ... Cl-氢键与Cl-抗衡离子紧密结合。ReOCl3（biimMe2）在湿丙酮（5％的水）中的水解导致线性的氧桥联双核物质[（OReCl2（biimMe2）2（mu-O）]含有螯合的biimMe2。仅含1％水的丙酮溶液会产生弯曲氧桥联双核物质[（OReCl2）2（mu-O）（mu-biimMe2）2]，其中每个Re中心保留ReO2Cl2N2配位，但biimMe2配体桥接。线性氧桥联[[（OReCl2（biimH2）2]由非甲基化的联咪唑获得的[（mu-O）]配合物包含两个通过NH ... Cl-氢键保持的Cl-离子，从而生成双阴离子[[OReCl2（biimH2
• Synthesis of cis- and trans-ReOMe2(bipy)Cl and related cationic oxorhenium(V) complexes
  作者：June-Ho Jung、Thomas A. Albright、David M. Hoffman、T. Randall Lee

  DOI：10.1039/a905835d

  日期：——

  The purpose of this study was to prepare high oxidation-state rhenium oxomethyl complexes, including cationic compounds, and test selected examples for olefin polymerization activity. Reaction of ReOMe2(PMe3)2Cl with pyridine N-oxide and 2,2′-bipyridine (bipy) gave cis-ReOMe2(bipy)Cl. Conversely, treatment of ReO(bipy)Cl3 with AlMe3 gave trans-ReOMe2(bipy)Cl. The compound cis-ReOMe2(bipy)Cl isomerized quantitatively to trans-ReOMe2(bipy)Cl upon heating in benzene (ΔH ‡ = 29(3) kcal mol–1, ΔS ‡ = 6(9) e.u.; at 79 °C, kobs = 1.34(9) × 10–2 min–1 and t1/2 = 52 min). Reaction of cis-ReOMe2(bipy)Cl with AgX (X– = PF6–, BF4–, or BPh4–) in acetonitrile gave the cationic acetonitrile adducts [ReOMe2(bipy)(CH3CN)]X. Treatment of the PF6– salt with PR3 (PR3 = PMe3, P(OMe)3, PMe2Ph, P(n-Bu)3, and PMePh2) yielded the cationic PR3 adducts cis-[ReOMe2(bipy)(PR3)][PF6]. The BF4– salt of the PMe3 adduct, cis-[ReOMe2(bipy)(PMe3)][BF4], was prepared by the reaction of ReOMe2(PMe3)2Cl with [Ag(CH3CN)2][BF4] in acetonitrile followed by treatment with bipy in CH2Cl2. Single crystal X-ray crystallographic analyses of cis-ReOMe2(bipy)Cl, trans-ReOMe2(bipy)Cl, and cis-[ReOMe2(bipy)(PMe3)][BF4] revealed that they have distorted octahedral structures. Analogs of cis-ReOMe2(bipy)Cl, trans-ReOMe2(bipy)Cl, and cis-[ReOMe2(bipy)(PMe3)][BF4] were also prepared in which the bipy ligand was replaced with 1,10-phenanthroline (phen). An additional analog of cis-[ReOMe2(bipy)(PMe3)][BF4] was prepared in which the bipy ligand was replaced by 4,4′-dimethyl-2,2′-bipyridine. In preliminary experiments, ethylene was polymerized using both cis-ReOMe2(bipy)Cl and trans-ReOMe2(bipy)Cl as catalyst precursors.

  本研究的目的是制备高氧化态铼氧甲基络合物（包括阳离子化合物），并测试选定实例的烯烃聚合活性。 ReOMe2(PMe3)2Cl 与吡啶 N-氧化物和 2,2'-联吡啶 (bipy) 反应，得到顺式 ReOMe2(bipy)Cl。相反，用 AlMe3 处理 ReO(bipy)Cl3 得到反式 ReOMe2(bipy)Cl。化合物 cis-ReOMe2(bipy)Cl 在苯中加热后定量异构化为反式 ReOMe2(bipy)Cl (ΔH ‡ = 29(3) kcal mol–1, ΔS ‡ = 6(9) e.u.；在 79 °C 时，kobs = 1.34(9) × 10–2 min–1 且 t1/2 = 52 min)。顺-ReOMe2(bipy)Cl 与 AgX (X– = PF6–、BF4– 或 BPh4–) 在乙腈中反应，得到阳离子乙腈加合物 [ReOMe2(bipy)(CH3CN)]X。用 PR3（PR3=PMe3、P(OMe)3、PMe2Ph、P(n-Bu)3 和 PMePh2）处理 PF6– 盐，产生阳离子 PR3 加合物 cis-[ReOMe2(bipy)(PR3)][PF6 ]。 PMe3 加合物的 -盐，顺式-[ReOMe2(bipy)(PMe3)][ ]，是通过 ReOMe2(PMe3)2Cl 与 [Ag(CH3CN)2][ ] 在乙腈中反应制备的，然后在 CH2Cl2 中用 bipy 处理。顺式-ReOMe2(bipy)Cl、反式-ReOMe2(bipy)Cl和顺式-[ReOMe2(bipy)(PMe3)][ ]的单晶X射线晶体分析表明它们具有扭曲的八面体结构。还制备了 cis-ReOMe2(bipy)Cl、trans-ReOMe2(bipy)Cl 和 cis-[ReOMe2(bipy)(PMe3)][ ] 的类似物，其中 bipy 配体被 1,10-菲咯啉取代（苯）。制备了顺式-[ReOMe2(bipy)(PMe3)][ ]的额外类似物，其中联吡啶配体被4,4'-二甲基-2,2'-联吡啶取代。在初步实验中，使用顺式ReOMe2(bipy)Cl和反式ReOMe2(bipy)Cl作为催化剂前体聚合乙烯。
• Herrmann, Wolfgang A,; Thiel, Werner R.; Herdtweck, Eberhartd, Chemische Berichte, 1990, vol. 123, # 2, p. 271 - 276
  作者：Herrmann, Wolfgang A,、Thiel, Werner R.、Herdtweck, Eberhartd

  DOI：——

  日期：——
• Bryan, Jeffrey C.; Stenkamp, Ronald E.; Tulip, Inorganic Chemistry, 1987, vol. 26, # 14, p. 2283 - 2288
  作者：Bryan, Jeffrey C.、Stenkamp, Ronald E.、Tulip、Mayer, James M.

  DOI：——

  日期：——