(CO)2ReNH(CH3)C2H4(η(5)-C5H4) | 187544-74-7

• 英文名称: (CO)2ReNH(CH3)C2H4(η(5)-C5H4)
• 英文别名: (η5:η1-C5H4CH2CH2NHMe)Re(CO)2
• CAS: 187544-74-7
• 化学式: C₁₀H₁₂NO₂Re
• 分子量: 364.418
• InChiKey: RYTHEELFCGGHTP-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：

  (CO)2ReNH(CH3)C2H4(η(5)-C5H4) 、 溴 在 pyridine 作用下， 以 二氯甲烷 为溶剂， 以82%的产率得到[(CO)2BrReNH(CH3)CH2CH2(η(5)-C5H4)]Br
  参考文献：
  名称：

  Insertion Reactions of CO into the Rhenium−Nitrogen Bond. η²-Carbamoyl Complexes and Their Reactions

  摘要：

  Deprotonation of [(CO)(2)RReNH(CH3)CH2CH2(eta(5)-C5H4)]X-+(-) (R = CO2Me, CO2Et; X = Br) followed by heating under a CO atmosphere yields the corresponding CO insertion compound (CO)(2)RReC(=O)N(CH3)CH2CH2(eta(5)-C5H4). An anologous insertion reaction proceeds more rapidly for the complexes [(CO)(2)XReNH(CH3)CH2CH2(eta(5) -C5H4)]Y-+(-) (X = Br, I, PhS, and PhSe) in which X is a strong electron-withdrawing group. Without the presence of external ligands, the oxygen of the resultant carbamoyl group binds to the rhenium to fulfill the 18-electron rule. The eta(2)-carbamoyl selenolate complex [(CO)PhSeRe(eta(2)-C=O)N(CH3)CH2CH2(eta(5)-C5H4)] (9b) has been characterized by X-ray crystallography. Upon addition of two-electron-donor ligands, such as CO, isocyanides, and trialkyl phosphites, the eta(2)-carbamoyl complexes convert cleanly to the corresponding eta(1)-carbamoyl complexes.

  DOI：

  10.1021/om970544i
• 作为产物：
  描述：

  (η(5)-C5H4CH2CH2NHCH3)Re(CO)3 以 四氢呋喃 为溶剂， 以64%的产率得到(CO)2ReNH(CH3)C2H4(η(5)-C5H4)
  参考文献：
  名称：

  Half-Sandwich Aminorhenium Complexes:  Preparation and Regioselective N-versus Re-Alkylations

  摘要：

  The aminorhenium complex (CO)(2)ReNH(CH3)CH2CH2(eta(5)-C5H4) (3), in which the ligating amino group is connected to the cyclopentadienyl ligand, was prepared by irradiation of (eta(5)-C5H4CH2CH2NHCH3)Re(CO)(3) (2) in THF. Alkylation of the corresponding anion [(CO)(2)ReN(CH3)CH2CH2(eta(5)-C5H4)]Li--(+) (4) as well as the neutral aminorhenium complex 3 with a variety of electrophiles has been studied. The anion 4 reacted with electrophiles, such as CH3I, CH2=CHCH2Br, C6H5CH2Br, and HC drop CCH2Br, at the nitrogen center to provide (CO)(2)ReNR(CH3)CH2CH2(eta(5)-C5H4) (5a-d). However, 4 reacted with electrophiles having a carbonyl group or a nitrile group next to the electrophilic carbon, such as BrCH2CO2CH3, BrCH2CO2C2H5, and BrCH2CN, to give rhenium alkylation compounds [(CO)(2)(R)ReNH(CH3)CH2CH2(eta(5)-C5H4)]Br-+(-) (7e-g) after protonation. The neutral aminorhenium complex 3 reacted with the electrophiles mentioned above to provide exclusive Re-alkylation compounds 7a-g. The structure of the tetraphenylborate salt of 7c, [(CO)(2)(C6H5CH2)ReNH(CH3)CH2CH2(eta(5)-C5H4)](+)BPh(4)(-) (8), has been determined by X-ray diffraction.

  DOI：

  10.1021/om960980p

文献信息

• Aminorhenium carbon dioxide complexes: formal oxidation of a carbon monoxide ligand with peroxy-acids or bromine/hydroxide
  作者：Tein-Fu Wang、Chong-Chen Hwu、Yuh-Sheng Wen

  DOI：10.1016/j.jorganchem.2003.09.051

  日期：2004.1

  confirmed by X-ray crystallography. The η2-CO2 complexes 4a–4d are stable at ambient temperature under air. In addition to peroxy-acid oxidation, bromination of the aminorhenium dicarbonyl complexes followed by base treatment also provided the corresponding η2-CO2 complexes. The reaction mechanism for the formation of CO2 complex from the corresponding dicarbonyl is discussed briefly.

  富电子aminorhenium络合物η 5：η 1 -C 5 ħ 4 CH 2 CH 2 NR（CH 3）的Re（CO）2（图3a - d ; R =甲基，苄基，Ñ丁基，Ñ丁基-OH ）很容易与过氧酸氧化以得到相应的η 2 -CO 2个络合物η 5：η 1 - Visual C 5 ħ 4 CH 2 CH 2 NR（CH 3）的Re（CO）（η 2 -CO 2）（4a - d）的收率很高。将所得η 2 -CO 2复杂主要是反式异构体。η的结构2 -CO 2复杂η 5 η：1 -C 5 ħ 4 CH 2 CH 2 N（CH 3）（ñ - Visual C 4 ħ 8 OH）的Re（CO）（η 2 -CO 2）（图4d -anti）和相应的CO配合物3d已通过X射线晶体学确认。的η 2 -CO 2配合物4a至4d在空气中的环境温度下是稳定的。除了过氧酸氧化作用，二羰aminorhenium络合物随后碱处理溴化还提供了相应的η
• Selective Reaction of Aminorhenium Complexes and the Formation of Cp‐N‐P Tridentate Complexes
  作者：Tein‐Fu Wang、Tan‐Ching Wang、Yuh‐Sheng Wen

  DOI：10.1002/ejic.200300650

  日期：2004.4

  provided a cationic heterocyclopropane complex 8 which reacted with various nucleophiles (tBuNH2, NaOCH3, KPPh2) to give precursors for tridentate complexes. A formal oxidation of the carbonyl ligand to a labile carbon dioxide ligand was accomplished by oxidation with peroxy acid. Intramolecular N ligand displacement furnished the Cp-N-P tridentate complex. The relative stability of the N, P and CO ligands

  已经以受控方式从环戊二烯基-氨基二齿配合物开始制备含有环戊二烯基-氨基-膦酰基三齿配体的铼配合物。[η5:η1-C5H4 NH(CH3)Re(CO)2Br]+ (2) 的脱溴化氢在低温下选择性地进行，得到环外亚铼配合物 [η5:η1-C5H4 N(=CH2)Re(CO)2] (5). 选择性 N-甲基化提供了一种阳离子杂环丙烷配合物 8，它与各种亲核试剂（tBuNH2、NaO 、KPPh2）反应，得到三齿配合物的前体。羰基配体正式氧化为不稳定的二氧化碳配体是通过用过氧酸氧化来完成的。分子内 N 配体置换提供了 Cp-NP 三齿复合物。当形成 η3-烯丙基配体时，揭示了 N、P 和 CO 配体的相对稳定性。随着 η1-烯丙基转化为相应的 η3-烯丙基配位模式，N 配体与金属而非 P 或 CO 配体分离。(© Wiley-VCH Verlag GmbH & Co. KGaA