dichlorooxoethoxobis(triphenylphosphine)rhenium(V) | 80227-22-1

• 英文名称: dichlorooxoethoxobis(triphenylphosphine)rhenium(V)
• 英文别名: (PPh₃)₂ReOCl₂(OEt)；ReOCl₂(OEt)(PPh₃)₂；ReO(OEt)Cl₂(PPh₃)₂；rhenium oxodichloroethoxybis(triphenylphosphine)；[ReOCl2(EtO)(PPh3)2]
• CAS: 80227-22-1
• 化学式: C₃₈H₃₅Cl₂O₂P₂Re
• 分子量: 842.755
• InChiKey: BCMMNHZHMNGCTJ-UHFFFAOYSA-L

计算性质

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

反应信息

• 作为反应物：
  描述：

  dichlorooxoethoxobis(triphenylphosphine)rhenium(V) 在 pyridine 作用下， 以 乙醇 为溶剂， 以95%的产率得到trans-dioxotetrakis(pyridine)rhenium(V) chloride dihydrate
  参考文献：
  名称：

  Synthesis, characterization and crystal structure of oxobis(p-thiocresolato)terpyridinerhenium(V), a new cationic, six-coordinate thiolato complex of rhenium

  摘要：

  The new six-coordinate rhenium(V) complex, oxobis(p-thiocresolato)terpyridinerhenium(V), was synthesized from [ReO2(py)4]CF3SO3 and characterized by elemental analysis, thin-layer chromatography, FAB mass spectroscopy, IR and H-1 NMR of the perrhenate salt, as well as by a single crystal X-ray structure determination of the hexafluorophosphate salt. This characterization establishes the structure of the complex in both solid state and solution to be the symmetrical mer(N,N,N),trans(S, S) species in which the central N atom of the terpyridine ligand is situated trans to the Re = O linkage. The X-ray and NMR studies demonstrate that the solution and solid state structures are identical.

  DOI：

  10.1016/s0020-1693(00)87352-1
• 作为产物：
  描述：

  ammonium perrhenate 在 P(C₆H₅)3 、 ethanol 、 HCl 作用下， 以 盐酸 、 乙醇 为溶剂， 以>99的产率得到dichlorooxoethoxobis(triphenylphosphine)rhenium(V)
  参考文献：
  名称：

  Synthesis, characterization and crystal structure of oxobis(p-thiocresolato)terpyridinerhenium(V), a new cationic, six-coordinate thiolato complex of rhenium

  摘要：

  The new six-coordinate rhenium(V) complex, oxobis(p-thiocresolato)terpyridinerhenium(V), was synthesized from [ReO2(py)4]CF3SO3 and characterized by elemental analysis, thin-layer chromatography, FAB mass spectroscopy, IR and H-1 NMR of the perrhenate salt, as well as by a single crystal X-ray structure determination of the hexafluorophosphate salt. This characterization establishes the structure of the complex in both solid state and solution to be the symmetrical mer(N,N,N),trans(S, S) species in which the central N atom of the terpyridine ligand is situated trans to the Re = O linkage. The X-ray and NMR studies demonstrate that the solution and solid state structures are identical.

  DOI：

  10.1016/s0020-1693(00)87352-1

文献信息

• Rhenium Chemistry of Diazabutadienes and Derived Iminoacetamides Spanning the Valence Domain II−VI. Synthesis, Characterization, and Metal-Promoted Regiospecific Imine Oxidation
  作者：Samir Das、Indranil Chakraborty、Animesh Chakravorty

  DOI：10.1021/ic034586c

  日期：2003.10.1

  4, respectively, where L' is the monoionized iminoacetamide ligand R'N=C(H)-C(=O)-NR'(-). Finally, the reaction of Re(V)O(OEt)X(2)(PPh(3))(2) with L has furnished bivalent species of type Re(II)X(2)(L)(2), 6(X = Cl, Br). The X-ray structures of 1 (R = Me, R' = Ph), 3 (R = H, R' = Ph, Ar = Ph), and 4 (R = H, R' = cycloheptyl, Ar = C(6)H(4)Cl) are reported revealing meridional geometry for the ReCl(3)

  R'N = C（R）-C（R）= NR'，L（R = H，Me; R'=环烷基，芳基）类型的二氮杂丁二烯与Re（V）OCl（3）（AsPh（ 3））（2）提供了Re（V）OCl（3）（L），1，其中Re（III）（OPPh（3））Cl（3）（L），2和Re（V）（ NAr）Cl（3）（L），3，已经合成。由H（2）O（2）水溶液对2（R = H）进行化学氧化，由稀HNO（3）对3（R = H）进行化学氧化，产生Re（IV）（OPPh（3））Cl（3）（ L'），5和Re（VI）（NAr）Cl（3）（L'），4，其中L'是单离子化亚氨基乙酰胺配体R'N = C（H）-C（= O）- NR'（-）。最后，Re（V）O（OEt）X（2）（PPh（3））（2）与L的反应提供了Re（II）X（2）（L）（2），6型二价物质（X ＝ Cl，Br）。1（R = Me，R'= Ph），3（R = H，R'=
• N–H cleavage as a route to new pincer complexes of high-valent rhenium
  作者：Alex J. Kosanovich、Wei-Chun Shih、Rodrigo Ramírez-Contreras、Oleg. V. Ozerov

  DOI：10.1039/c6dt03640f

  日期：——

  A novel PNN-type pincer ligand has been accessed via imine reduction with LiAlH4 to provide the phosphine diamino proligand, PNHNH (1). The ligand, 1, as well as PNHP can be metallated directly, via N–H cleavage, with L2ReOX2(OEt) precursors to access six-coordinate (PNP)ReOCl2 (2) and (PNNH)ReOX2 (3-Cl, X = Cl; 3-Br, X = Br) in good yield. 3-Cl and 3-Br undergo dehydrohalogenation upon treatment with

  一种新的PNN型钳式配体已通过使用LiAlH 4的亚胺还原得到，以提供膦二氨基配体PN H N H（1）。配体1和PN H P可以通过N–H裂解直接与L 2 ReOX 2（OEt）前体金属化，从而获得六配位（PNP）ReOCl 2（2）和（PNN H）ReOX 2（3-Cl，X ＝ Cl；3-Br，X ＝ Br）以良好的收率。3-Cl和3-Br经NEt 3处理后进行脱卤化氢反应，以优异的收率提供了五配位的膦/二酰胺PNN型化合物（PNN）ReOX（4-Cl，X = Cl; 4-Br，X = Br），以混合形式存在旋转异构体。在分别与HCl （aq）和PMe 3分别提供3-Cl和4-PMe 3的反应中，显示了这种去质子的可逆性和4-Cl的配位不饱和。用AgOAc，AgOTf或NaHBEt 3处理4-Cl导致形成（PNN）ReO（OAc）（4-OAc），（PNN）ReO（OTf）（4-OTf）
• Irreversible Hydrolysis of PCP-Supported Rhenium(V) Acetates
  作者：Alex J. Kosanovich、Wei-Chun Shih、Oleg V. Ozerov

  DOI：10.1021/acs.inorgchem.7b02628

  日期：2018.1.16

  Complexes (PCPR)Re(O)(OAc)2 [R = iPr (4a) and tBu (4b); PCP = κ3-P,C,P-2,6-(R2PCH2)2C6H3] undergo unexpected irreversible hydrolysis to yield (PCPR)Re(O)(OAc)(OH) (3a/3b) and free AcOH. 3a and 3b are highly fluxional in solution, possibly via AcOH loss and the intermediacy of (PCPR)Re(O)2, which was isolated for R = tBu (5b).

  络合物（PCP R）Re（O）（OAc）2 [R = i Pr（4a）和t Bu（4b）; PCP =κ 3 - P，Ç，P -2,6-（R 2 PCH 2）2 C ^ 6 ħ 3 ]经历意外的不可逆的水解，得到（PCP ř）回复（O）（OAc）（OH）（3A / 3b）和游离的AcOH。3a和3b在溶液中的流动性很高，可能是由于AcOH损失和（PCP R）Re（O）的中间性2，对于R = t Bu（5b）被隔离。
• Structural and Spectroscopic Characterization of Rhenium Complexes Containing Neutral, Monoanionic, and Dianionic Ligands of 2,2′-Bipyridines and 2,2′:6,2″-Terpyridines: An Experimental and Density Functional Theory (DFT)-Computational Study
  作者：Mei Wang、Thomas Weyhermüller、Eckhard Bill、Shengfa Ye、Karl Wieghardt

  DOI：10.1021/acs.inorgchem.6b00609

  日期：2016.5.16

  (Mebpy = 4, 4′-dimethyl-2,2′-bipyridine; Tp– = tris-pyrazolylborate, tpy = 2, 2′:6, 2″-terpyridine). For each series we show that the average Cpy–Cpy bond length and the average C–Nchel bond distance vary in a linear fashion with the charge n of the N,N′-coordinated (bpy)n and N,N′,N″-coordinated (tpy)n ligand. Consequently, the difference Δ between these two bond lengths varies also linearly with n. Δ is

  以下电子转移系列成员的分子和电子结构已通过单晶X射线晶体学，与温度相关的磁化率测量以及UV-vis-NIR和电子顺磁共振光谱法确定，并通过密度泛函理论计算得到了验证（ DFT B3LYP）：[Re（Me bpy）3 ] n，[Re（tpy）2 ] n，[Re（Tp）（bpy）Cl] n（n = 2 +，1 +，0、1-）和[Re（bpy）（CO）3 ] 1 +，0,1–（Me bpy = 4，4'-二甲基-2,2'-联吡啶; Tp –=三吡唑基硼酸酯，tpy = 2、2'：6、2''-叔吡啶）。对于每个系列，我们表明平均C py –C py键长和平均C–N chel键距离随着N，N'配位（bpy）n和N，N'的电荷n线性变化。，N”-配位的（tpy）n配体。因此，这两个键长之间的差Δ也随n线性变化。Δ被证明是这两个杂环配体（中性，π-自由基阴离子和二价阴离子）氧化水平的有用单一标记。此外，
• Synthesis, characterization and molecular structure of oxo and phenylimido rhenium(V) complexes of 1-phenyl-2-(diisopropylphosphino)-ethanone
  作者：Xavier Couillens、Marie Gressier、Michèle Dartiguenave

  DOI：10.1016/s0020-1693(02)01198-2

  日期：2003.1

  New rhenium-oxo and phenylimido complexes were synthetized and isolated by reaction of 1-phenyl-2-(diisopropylphosphino)ethanone on ReOX3(PPh3)2 (X=Cl, Br, I), ReO(OEt)Cl2(PPh3)2 and Re(NPh)Cl3(PPh3)2 in basic media (NEt3). In these complexes the ligand bonds mainly as monoanionic enolato chelating agent. The reactions are solvent dependent. The disubstituted ReOX(PO)2 compounds (1–7) adopt a ‘twisted’

  通过1-苯基-2-（二异丙基膦基）乙酮在ReOX 3（PPh 3）2（X = Cl，Br，I），ReO（OEt）Cl 2（PPh 3）2和Re（NPh）Cl 3（PPh 3）2在碱性介质（NEt 3）中。在这些络合物中，配体键主要作为单阴离子烯醇螯合剂。反应取决于溶剂。双取代的再氧化（PO）2份的化合物（1 - 7）采取“扭曲”八面体结构与的混合物顺-PP和反式-PP在甲苯中的构型，因此表明在这种情况下，两种非对映异构体之间的稳定性差距很小。在乙醇中，仅观察到“扭曲的”顺式-PP构象构型ReOCl（PO）2（1）和ReO（OEt）（PO）2（7）。当X = Br和I时，分离出的独特物种是由卤代乙氧基立体选择性取代乙氧基生成的乙氧基-羰基复合物ReO（OEt）（PO）2（7）。与Re（NPh）Cl的反应3（PPh 3）2的选择性较低，在乙醇中，需要过量的配体才能获得反式-PP-Re（