trans-[Mn(depe)2(CCSiEt3)2] | 856019-53-9

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: trans-[Mn(depe)2(CCSiEt3)2]
• 英文别名: trans-[Mn(bis(diethylphosphino)ethane)2(CCSiEt3)2]
• CAS: 856019-53-9
• 化学式: C₃₆H₇₈MnP₄Si₂
• 分子量: 746.019
• InChiKey: YZYMJSPNQYSDTH-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：

  ferrocenium hexafluorophosphate 、 trans-[Mn(depe)2(CCSiEt3)2] 以 二氯甲烷 为溶剂， 以90%的产率得到[Mn(depe)2(CCSiEt3)2][PF6]
  参考文献：
  名称：

  Synthesis and Characterization of Redox-Active C₄-Bridged Rigid-Rod Complexes with Acetylide-Substituted Manganese End Groups

  摘要：

  The symmetric d(5) trans-bis(alkynyl) complexes [Mn(R'2PCH2CH2PR'(2))(2)(C CR)(2)] (R'= Me, R = SiEt3, 3a; R' = Me, R = (SiPr3)-Pr-i, 3b; R' = Me, R = Si(Bu-t)Me-2, 3c; R' = Et, R = SiEt3, 4a; R' = Et, R = (SiPr3)-Pr-i, 4b; R' = Et, R = Si(Bu-t)Me-2, 4c) can be prepared by the reaction of [Mn(R'2PCH2CH2PR'(2))(2)Br-2] (R' = Me, 1; R' = Et, 2) with 2 equiv of LiC CR (R = SiEt3, (SiPr3)-Pr-i, Si(Bu-t)Me-2). The reactions of species 3 and 4 with [Cp2Fe] [PF6] yield the corresponding d4 complexes [Mn(dmpe)(2)(C CR)(2)] [PF6] (R' = Me, R = SiEt3, 5a; R' = Me, R = (SiPr3)-Pr-i, 5b; R' = Me, R = Si(Bu-t)Me-2, 5c; R' = Et, R = SiEt3, 6a; R' = Et, R = (SiPr3)-Pr-i, 6b; R' = Et, R = Si(Bu-t)Me-2, 6c). The asymmetrically substituted trans-bis(alkynyl) complexes [Mn(dmpe)(2)(C CR)(C CH)] [PF6] (R' = Me, R = SiEt3, 10a; R' = Me, R = (SiPr3)-Pr-i, 10b; R' = Me, R = Si(Bu-t)Me-2, 10c) are prepared by the reaction of the vinylidene compounds Mn(dmpe)(2)(C CR)(C CH2) (R' = Me, R = SiEt3, 9a; R' = Me, R = (SiPr3)-Pr-i, 9b; R' = Me, R = Si(Bu-t)Me-2, 9c) with 2 equiv of [Cp2Fe] [PF6] and 1 equiv of quinuclidine. The mixed-valent complexes [{Mn(dmpe)(2)(C CR)}(2)(mu-C-4)] [PF6] [11](+) are obtained by the reaction of 10 with 1 equiv of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The neutral dinuclear Mn(II)/Mn(II) compounds [{Mn(dmpe)(2)(C CR)}(2)(mu-C-4)] (R = SiEt3, 11a; R = (SiPr3)-Pr-i, 11b; R = Si(Bu-t)Me-2, 11c) are synthesized by the reduction of [11](+) with Co(C5Me5)(2). Complexes [11](+) can also be oxidized with [Cp2-Fe] [PF6] to produce the dicationic Mn(III)/Mn(III) species [{Mn(dmpe)(2)(C CR3)}(2)(mu-C-4)] [PF6](2) (R = SiEt3, [11a](2+); R = (SiPr3)-Pr-i, [11b](2+); R = Si(Bu-t)Me-2, [11c](2+)). Both redox processes are fully reversible. The dinuclear compounds have been characterized by NMR, IR, and Raman spectroscopy, cyclic voltammetry, and elemental analyses. X-ray diffraction studies have also been performed on several complexes.

  DOI：

  10.1021/om049252p
• 作为产物：
  描述：

  [Mn(depe)Br2] 、 (triethylsilyl)ethynyl lithium 以 四氢呋喃 为溶剂， 以80%的产率得到trans-[Mn(depe)2(CCSiEt3)2]
  参考文献：
  名称：

  Synthesis and Characterization of Redox-Active C₄-Bridged Rigid-Rod Complexes with Acetylide-Substituted Manganese End Groups

  摘要：

  The symmetric d(5) trans-bis(alkynyl) complexes [Mn(R'2PCH2CH2PR'(2))(2)(C CR)(2)] (R'= Me, R = SiEt3, 3a; R' = Me, R = (SiPr3)-Pr-i, 3b; R' = Me, R = Si(Bu-t)Me-2, 3c; R' = Et, R = SiEt3, 4a; R' = Et, R = (SiPr3)-Pr-i, 4b; R' = Et, R = Si(Bu-t)Me-2, 4c) can be prepared by the reaction of [Mn(R'2PCH2CH2PR'(2))(2)Br-2] (R' = Me, 1; R' = Et, 2) with 2 equiv of LiC CR (R = SiEt3, (SiPr3)-Pr-i, Si(Bu-t)Me-2). The reactions of species 3 and 4 with [Cp2Fe] [PF6] yield the corresponding d4 complexes [Mn(dmpe)(2)(C CR)(2)] [PF6] (R' = Me, R = SiEt3, 5a; R' = Me, R = (SiPr3)-Pr-i, 5b; R' = Me, R = Si(Bu-t)Me-2, 5c; R' = Et, R = SiEt3, 6a; R' = Et, R = (SiPr3)-Pr-i, 6b; R' = Et, R = Si(Bu-t)Me-2, 6c). The asymmetrically substituted trans-bis(alkynyl) complexes [Mn(dmpe)(2)(C CR)(C CH)] [PF6] (R' = Me, R = SiEt3, 10a; R' = Me, R = (SiPr3)-Pr-i, 10b; R' = Me, R = Si(Bu-t)Me-2, 10c) are prepared by the reaction of the vinylidene compounds Mn(dmpe)(2)(C CR)(C CH2) (R' = Me, R = SiEt3, 9a; R' = Me, R = (SiPr3)-Pr-i, 9b; R' = Me, R = Si(Bu-t)Me-2, 9c) with 2 equiv of [Cp2Fe] [PF6] and 1 equiv of quinuclidine. The mixed-valent complexes [{Mn(dmpe)(2)(C CR)}(2)(mu-C-4)] [PF6] [11](+) are obtained by the reaction of 10 with 1 equiv of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The neutral dinuclear Mn(II)/Mn(II) compounds [{Mn(dmpe)(2)(C CR)}(2)(mu-C-4)] (R = SiEt3, 11a; R = (SiPr3)-Pr-i, 11b; R = Si(Bu-t)Me-2, 11c) are synthesized by the reduction of [11](+) with Co(C5Me5)(2). Complexes [11](+) can also be oxidized with [Cp2-Fe] [PF6] to produce the dicationic Mn(III)/Mn(III) species [{Mn(dmpe)(2)(C CR3)}(2)(mu-C-4)] [PF6](2) (R = SiEt3, [11a](2+); R = (SiPr3)-Pr-i, [11b](2+); R = Si(Bu-t)Me-2, [11c](2+)). Both redox processes are fully reversible. The dinuclear compounds have been characterized by NMR, IR, and Raman spectroscopy, cyclic voltammetry, and elemental analyses. X-ray diffraction studies have also been performed on several complexes.

  DOI：

  10.1021/om049252p