| 188842-46-8

• CAS: 188842-46-8
• 化学式: C₇H₅CrF₆NO₇S₂*C₁₆H₃₆N
• 分子量: 687.706
• InChiKey: DXGPSNXSPQSVRW-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：
  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：

  、 potassium bromide 以 二氯甲烷 为溶剂， 以62%的产率得到
  参考文献：
  名称：

  Synthesis and Characterization of 17-Valence-Electron [CpCr(NO)X₂]^- Anions:  Oxidatively Induced Loss of the Nitrosyl Ligand¹

  摘要：

  Several anionic and paramagnetic [CpCr(NO)X-2](-) complexes (X = I [1], O3SCF3 (OTf) [2], Br [3], Cl [4]) have been prepared as potential precursors to neutral CpCr(NO)X-2 species. Reaction of [CpCr(NO)I](2) with [NBu4]I provides [NBu4][1], and halide abstraction from [NBu4][1] with 2 equiv of AgOTf affords [NBu4][2]. The weakly-bound OTf- ligands of [NBu4][2] are readily displaced by Br- to produce [NBu4][3]. The dichloro complexes [NEt4][4] and [PPN][4] are obtained by treating [CpCr(NO)Cl](2) with [NE4]Cl and [PPN]Cl, respectively. Use of acetonitrile as reaction solvent allows generation of the requisite [CpCr(NO)Cl](2) directly from CpCr(NO)(CO)(2) and PCl5, a marked improvement over previous synthetic routes to this dimer. Similar halogenations of Cp*Cr(NO)(CO)(2) in NCMe provide access to the previously unknown [Cp*Cr(NO)I](2) (5), and [Cp*Cr(NO)Cl](2) (6), halo-bridged, and dimers. The solid-state molecular structure of [PPN][4]. CH2Cl2 has been established by single-crystal X-ray crystallography to be a normal three-legged piano stool. The one-electron oxidation of [4] has been investigated both chemically (by reaction with [Cp2Fe](+)) and electrochemically (by cyclic voltammetry). These studies suggest that upon oxidation a high-spin CpCr(NO)Cl-2 complex is initially formed which then rapidly releases NO. Extended Huckel molecular-orbital calculations have been performed on [4], [CpCr(CO)(3)](-), and [CpCrCl3](-), three CpCr-containing anions with ligands of varying pi-bonding capabilities. Correlations between their orbital energies and electron occupancies and a rationale for the lability of the NO ligand in neutral CpCr(NO)Cl-2 are provided.

  DOI：

  10.1021/ja963464z
• 作为产物：
  描述：

  、 silver trifluoromethanesulfonate 、 四丁基碘化铵 以 二氯甲烷 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  Synthesis and Characterization of 17-Valence-Electron [CpCr(NO)X₂]^- Anions:  Oxidatively Induced Loss of the Nitrosyl Ligand¹

  摘要：

  Several anionic and paramagnetic [CpCr(NO)X-2](-) complexes (X = I [1], O3SCF3 (OTf) [2], Br [3], Cl [4]) have been prepared as potential precursors to neutral CpCr(NO)X-2 species. Reaction of [CpCr(NO)I](2) with [NBu4]I provides [NBu4][1], and halide abstraction from [NBu4][1] with 2 equiv of AgOTf affords [NBu4][2]. The weakly-bound OTf- ligands of [NBu4][2] are readily displaced by Br- to produce [NBu4][3]. The dichloro complexes [NEt4][4] and [PPN][4] are obtained by treating [CpCr(NO)Cl](2) with [NE4]Cl and [PPN]Cl, respectively. Use of acetonitrile as reaction solvent allows generation of the requisite [CpCr(NO)Cl](2) directly from CpCr(NO)(CO)(2) and PCl5, a marked improvement over previous synthetic routes to this dimer. Similar halogenations of Cp*Cr(NO)(CO)(2) in NCMe provide access to the previously unknown [Cp*Cr(NO)I](2) (5), and [Cp*Cr(NO)Cl](2) (6), halo-bridged, and dimers. The solid-state molecular structure of [PPN][4]. CH2Cl2 has been established by single-crystal X-ray crystallography to be a normal three-legged piano stool. The one-electron oxidation of [4] has been investigated both chemically (by reaction with [Cp2Fe](+)) and electrochemically (by cyclic voltammetry). These studies suggest that upon oxidation a high-spin CpCr(NO)Cl-2 complex is initially formed which then rapidly releases NO. Extended Huckel molecular-orbital calculations have been performed on [4], [CpCr(CO)(3)](-), and [CpCrCl3](-), three CpCr-containing anions with ligands of varying pi-bonding capabilities. Correlations between their orbital energies and electron occupancies and a rationale for the lability of the NO ligand in neutral CpCr(NO)Cl-2 are provided.

  DOI：

  10.1021/ja963464z

文献信息

• Cyclopentadienyl nitrosyl compounds of chromium: aqueous solution chemistry, π bonding and nitric oxide loss
  作者：Peter Legzdins、Steven J. Rettig、Kevin M. Smith、Vicki Tong、Victor G. Young Jr

  DOI：10.1039/a703595k

  日期：——

  The complex [Cr(η-C 5 H 5 )(NO) 2 (CF 3 SO 3 )] 1 was synthesised in order to explore the relationship between π-donor ligands and nitrosyl lability and to investigate the aqueous chemistry of the [Cr(η-C 5 H 5 )(NO) 2 ] + fragment. Treatment of 1 with σ-donor ligands gave [Cr(η-C 5 H 5 )(NO) 2 (L)][CF 3 SO 3 ] salts. Potentiometric titrations and 1 H NMR spectroscopic studies of 1 provided evidence for the existence of [Cr(η-C 5 H 5 )(NO) 2 (H 2 O)] + and [Cr(η-C 5 H 5 )(NO) 2 (OH)] in aqueous solution. When generated in situ, [Cr(η-C 5 H 5 )(NO) 2 (OH)] reacted with acetylacetone, pyridinecarboxylic acid, or salicylaldehyde to form paramagnetic, mononitrosyl complexes, which were independently synthesised from the mononitrosyl precursor [Cr(η-C 5 H 5 )(NO)(µ-I)] 2 . The solid-state molecular structures of [Cr(η-C 5 Me 5 )(NO) 2 (CF 3 SO 3 )] 2, [Cr(η-C 5 H 5 )(NO) 2 (N 2 C 5 H 7 )] 9 and [Cr(η-C 5 H 5 )(NO)(O 2 C 5 H 7 )] 10 were determined by X-ray crystallography. Crystals of 2 are monoclinic, a = 8.575(1), b = 8.642(1), c = 21.8626(9) Å, β = 91.760(7)°, Z = 4, space group P2 1 /n; crystals of 9 are monoclinic, a = 18.3382(4), b = 11.1774(3), c = 12.9102(1) Å, β = 121.386(1)°, Z = 8, space group C2/c; and those of 10 are orthorhombic, a = 17.373(2), b = 8.833(1), c = 6.926(2) Å, Z = 4, space group Pnma.

  合成复合物 [Cr(δ--C 5 H 5 )(NO) 2 (CF 3 SO 3 )] 1 的目的是为了探索 Ï-供体配体与亚硝基易化性之间的关系，并研究 [Cr(δ--C 5 H 5 )(NO) 2 ] + 片段的水化学性质。用Ï-供体配体处理 1 得到[Cr(δ--C 5 H 5 )(NO) 2 (L)][CF 3 SO 3 ]盐。对 1 的电位滴定和 1 H NMR 光谱研究证明，水溶液中存在 [Cr(δ--C 5 H 5 )(NO) 2 (H 2 O)] + 和 [Cr(δ--C 5 H 5 )(NO) 2 (OH)] 。原位生成时，[Cr(δ--C 5 H 5 )(NO) 2 (OH)] 与乙酰丙酮、吡啶甲酸或水杨醛反应，形成顺磁性的单亚硝基络合物，这些络合物是由单亚硝基前体[Cr(δ--C 5 H 5 )(NO)(µ-I)] 2 单独合成的。 通过 X 射线晶体学测定了[Cr(δ--C 5 Me 5 )(NO) 2 (CF 3 SO 3 )] 2、[Cr(δ--C 5 H 5 )(NO) 2 (N 2 C 5 H 7 )] 9 和[Cr(δ--C 5 H 5 )(NO)(O 2 C 5 H 7 )] 10 的固态分子结构。2 的晶体为单斜晶系，a = 8.575(1)，b = 8.642(1)，c = 21.8626(9) à ，δ = 91.760(7)° ，Z = 4，空间群 P2 1 /n；9 的晶体为单斜晶系，a = 18.3382(4)，b = 11.1774(3), c = 12.9102(1) à , δ² = 121.386(1)°, Z = 8, 空间群 C2/c；10 的晶体为正方晶系，a = 17.373(2), b = 8.833(1), c = 6.926(2) à , Z = 4, 空间群 Pnma。