| 31960-39-1

• CAS: 31960-39-1
• 化学式: BF₄*C₇H₅MnNO₃
• 分子量: 292.864
• InChiKey: XAJSIGRDPVGZLA-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：

  、 N,N-tetraethyldiamidothiophosphite S-ethyl 以 丙酮 为溶剂， 生成
  参考文献：
  名称：

  Sinyashin, O. G.; Gorshunov, I. Yu.; Milyukov, V. A., Russian Journal of General Chemistry, 1994, vol. 64, # 2.1, p. 226 - 230

  摘要：

  DOI：

文献信息

• Dppa als Komplexligand: Metall-Koordination und P-N-Spaltung in Komplexen des Typs [CpM(L)dppa]X (M = Fe, Mn; L = CO, NO) / Dppa as a Ligand: Metal Coordination and P-N Cleavage in Complexes of the Type [CpM(L)dppa]X (M = Fe, Mn; L = CO, NO)
  作者：Jan Geicke、Ingo-Peter Lorenz、Petra Mürschel、Kurt Polbom

  DOI：10.1515/znb-1997-0509

  日期：1997.5.1

  The reactions of [CpMn(CO)₂(NO)]BF₄ or CpFe(CO)₂Cl with PPh₂NHR (R = Ph, PPh₂) lead to the salts [CpML(CO)PPh₂NHR]X with monodentate aminophosphine ligands. In the case of R = PPh₂ (= dppa) the complexes [CpML(dppa)]X with bidentate dppa are also formed. The salt [CpFe(CO)(dppa)]Cl can be deprotonated to give the neutral complex CpFe(CO)(PPh₂)₂N)} with the diphosphinoamide ligand, which can be N-alkylated by Mel to afford [CpFe(CO)(PPh₂)₂NMe}]I. The complex [CpMn(NO)(dppa)]BF₄ undergoes a P-N cleavage reaction by the solvent methanol to form [CpMn(NO)(PPh₂NH₂)(PPh₂OMe)]BF₄. The non-chelated complexes [CpFe(CO)₂PPh₂NHR]Cl are deprotonated by DBU to give the neutral ferrioiminophosphoranes CpFe(CO)₂PPh2 = NR. For R = PPh2 photolysis leads to CO-elimination and to CpFe(CO)(PPh₂NPPh₂). CpFe(CO)₂PPh₂NPPh₂ can be alkylated by Mel or metallated by CpFe(CO)₂Cl to form [CpFe(CO)₂PPh₂NPPh₂Me]I or [CpFe(CO)₂PPh₂NPPh₂(CO)₂FeCp]Cl, respectively. Oxidation of CpFe(CO)₂PPh₂NPPh₂ is possible by (SiMe₃)₂O₂, sulfur, or selenium to lead to the neutral complexes CpFe(CO)₂PPh₂=NPPh₂ = E (E = O, S, Se) with a heterodiene system. The IR and NMR spectra of all species as well as the X-ray structures of the complexes [CpFe(CO)dppa]Cl, [CpMn(NO)dppa]BF₄ and [CpMn(NO)(PPh₂NH₂)(PPh₂OMe)]BF₄ are reported and discussed.

  摘要：[CpMn(CO)2(NO)]BF4或CpFe(CO)2Cl与PPh2NHR（R = Ph，PPh2）的反应导致具有单齿氨基膦配体的盐[CpML(CO)PPh2NHR]X的形成。在R = PPh2（= dppa）的情况下，还形成了具有双齿dppa的配合物[CpML(dppa)]X。盐[CpFe(CO)(dppa)]Cl可以去质子化形成中性配合物CpFe(CO)(PPh2)2N)}，该配合物可以被Mel N-烷基化以得到[CpFe(CO)(PPh2)2NMe}]I。配合物[CpMn(NO)(dppa)]BF4通过溶剂甲醇发生P-N解离反应，形成[CpMn(NO)(PPh2NH2)(PPh2OMe)]BF4。非螯合配合物[CpFe(CO)2PPh2NHR]Cl经DBU去质子化形成中性的ferrioiminophosphoranes CpFe(CO)2PPh2=NR。对于R = PPh2，光解导致CO消除并形成CpFe(CO)(PPh2NPPh2)。CpFe(CO)2PPh2NPPh2可以被Mel烷基化或被CpFe(CO)2Cl金属化形成[CpFe(CO)2PPh2NPPh2Me]I或[CpFe(CO)2PPh2NPPh2(CO)2FeCp]Cl。通过(SiMe3)2O2、硫或硒氧化CpFe(CO)2PPh2NPPh2是可能的，以形成具有杂二烯系统的中性配合物CpFe(CO)2PPh2=NPPh2=E（E = O、S、Se）。所有物种的红外和核磁共振光谱以及配合物[CpFe(CO)dppa]Cl、[CpMn(NO)dppa]BF4和[CpMn(NO)(PPh2NH2)(PPh2OMe)]BF4的X射线结构已报告并讨论。
• Synthesis, structure and reactivity of (.eta.5-cyclopentadienyl)nitrosylcobalt
  作者：Wayne P. Weiner、Frederick J. Hollander、Robert G. Bergman

  DOI：10.1021/ja00336a027

  日期：1984.11

  Synthese par reaction de (CpCoNO) 2 avec Na/Hg dans Et 2 O. On prepare egalement NaMeCpCoNO. Reaction du cobaltate avec R 3 SnCl donnant les complexes CpCo(NO)SnR 3

  合成这些标准反应 de (CpCoNO) 2 avec Na/Hg dans Et 2 O。在制备 egalement NaMeCpCoNO。反应二钴酸盐 avec R 3 SnCl donnant les complexes CpCo(NO)SnR 3
• Manganiophosphonium-Salze: Synthese, Eigenschaften und Struktur von Komplexen des Typs [CpMn(CO)(NO)PPh₂H]BF₄ und [Cp′Mn(CO)(NO)PPh₂R]X (R = H, CH₃, {CpMn(CO)(NO)}; X = BF₄, PF₆)
  作者：Stefan Rudolph、Jan Geicke、Ingo Peter Lorenz、Thomas Seifert、Kurt Polborn、Manfredo Hörner

  DOI：10.1515/znb-2003-0611

  日期：2003.6.1

  The reaction of [Cp′Mn(CO)₂NO]X (Cp = C₅H₅, C₅H₄Me = Cp′; X =BF₄, PF₆) with PPh₂H leads to the formation of the diphenylmanganiophosphonium salts [CpMn(CO)NO}PPh₂H]X, which can be deprotonated by DABCO to give the not isolable manganiophosphane CpMn(CO)NO}PPh₂. This reactive intermediate, however, can be methylated by MeI and CF₃SO₃Me or organometallated by C₅H₅Fe(CO)₂Cl to yield the phosphonium salts [Cp′Mn(CO)NO}PPh₂Me]PF₆ and [Cp′Mn(CO)NO}PPh₂C₅H₅Fe(CO)₂}]PF₆, respectively. The methyl derivative is deprotonated by ^πBuLi to give the unstable methylene phosphorane Cp′Mn(CO)NO}PPh₂=CH₂, an organometallated phosphorus ylide. The in situ from [Cp′Mn(CO)NO}PPh₂H]BF₄ generated phosphane Cp′Mn(CO)NO}PPh₂ is oxidized by epoxycyclohexane to give the intermediate oxophosphorane Cp′Mn(CO)NO}P(O)Ph₂, which reacts with the still available starting material to yield the first dimanganiodiphenylphosphonium salt [Cp′Mn(CO)NO}₂PPh₂]BF₄. The compounds have been characterized by spectroscopic (IR, NMR, MS), analytical (C, H, N) and X-ray diffraction investigations ([C₅H₅Mn(CO)NO}PPh₂H]BF₄, [Cp′Mn(CO)NO}PPh₂Me]BF₆, [Cp′Mn(CO)NO}₂PPh₂]-BF₄).

  [Cp′Mn(CO)2NO]X（Cp = C5H5，C5H4Me = Cp′; X = BF4，PF6）与PPh2H反应，形成二苯基锰膦盐[CpMn(CO)NO}PPh2H]X，可被DABCO去质子化，得到不可分离的锰膦化合物CpMn(CO)NO}PPh2。然而，这种反应中间体可以被MeI和CF3SO3Me甲基化，或被 Fe(CO)2Cl有机金属化，分别生成膦盐[Cp′Mn(CO)NO}PPh2Me]PF6和[Cp′Mn(CO)NO}PPh2 Fe(CO)2}]PF6。甲基衍生物可以被πBuLi去质子化，生成不稳定的亚甲基膦酰烯Cp′Mn(CO)NO}PPh2=CH2，一种有机金属磷叉化合物。由[Cp′Mn(CO)NO}PPh2H] 生成的膦化合物Cp′Mn(CO)NO}PPh2在环氧环己烷氧化作用下生成中间体氧代膦酰烯Cp′Mn(CO)NO}P(O)Ph2，后者与仍可用的起始物质反应，生成第一个二锰双苯基膦盐[Cp′Mn(CO)NO}2PPh2] 。这些化合物已通过光谱（IR，NMR，MS），分析（C，H，N）和X射线衍射研究（[ Mn(CO)NO}PPh2H] ，[Cp′Mn(CO)NO}PPh2Me]BF6，[Cp′Mn(CO)NO}2PPh2]- ）进行了表征。
• Reactions of Thioesters of Phosphorus Acids with Cationic Complexes of Manganese
  作者：Oleg Sinyashin、Vasily Milyukov、Alexandr Zverev、Alexandr Plyamovatyi、Raviya Mukhamadeeva、Elvira Batyeva、Allan Ginzburg、Vyacheslav Sokolov

  DOI：10.1080/10426509608545109

  日期：——
• Comparison of the neutral benzyldiphenylphosphine complexes C6H6Cr(CO)2PPh2Bz and C5H5Mn(CO)2PPh2Bz with the isoelectronic manganiobenzyldiphenylphosphonium salts [C5R5Mn(CO)(NO)PPh2Bz]BF4
  作者：J. Geicke、I.-P. Lorenz、K. Polborn

  DOI：10.1016/s0020-1693(97)05873-8

  日期：1998.5

  The photolytically or thermally induced substitution reactions of C6C6(CO)(3), C5H5Mn(CO)(3) or [C5R5Mn(CO)(2)(NO)]BF4 (R = H CH3) with PPh(2)Bz led to isoelectronic benzyldiphenylphosphine complexes of half sandwich type C6H6Cr(CO)(2)PPh(2)Bz (1), C5H5Mn(CO)(2)PPh(2)Bz (2), [C5H5Mn(CO)(NO)(PPh(2)Bz)]BF4 (3a) and [C5Me5Mn(CO)(NO)(PPh(2)Bz)] BF4 (3b). In contrast to the neutral compounds 1 and 2, the phosphonium salts 3a, 3b can be deprotonated at the alpha-methylene group by bases such as DBU and LDA to give the neutral manganiodiphenylalkylidenephosphoranes C5R5Mn(CO)(NO)(PPh2=CHPh) (4a, 4b). H-1-, C-13-, P-31H-1}-NMR, IR and mass spectra of 1-4 are given. Crystals of 1 are orthorhombic, space group Pbca, with a = 19.960(3), b = 16.599(3) and c = 14.573(3) Angstrom, Z = 8 and R = 0.0521 for 2433 observed reflections. Crystals of 2 and 3a are monoclinic, space group P21/c, with a = 9.730(3), b = 23.123(6) and c = 9.784(3) Angstrom, Z = 4 and R = 0.0430 for 2512 observed reflections for 2, and a = 12.457(3), b = 10.597(3) and c = 18.764(5) Angstrom, Z = 4 and R = 0.0477 for 2765 observed reflections for 3a. (C) 1998 Elsevier Science S.A. All rights reserved.