[K(18-crown-6)(DMF)2][Ir(acetonitrile)(Se4)2] | 184244-02-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [K(18-crown-6)(DMF)2][Ir(acetonitrile)(Se4)2]
• CAS: 184244-02-8
• 化学式: C₄H₆IrN₂Se₈*C₁₈H₃₈KN₂O₈
• 分子量: 1355.61
• InChiKey: CGTNQXQVUMQDHO-UHFFFAOYSA-J

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：

  selenium 、 [K(18-crown-6)(DMF)2][Ir(acetonitrile)(Se4)2] 在 LiBEt₃H 作用下， 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Group 9 Chalcogenometalates

  摘要：

  The compounds [K(18-crown-6)](3)[Ir(Se-4)3] (1), [K(2.2.2-cryptand)](3)[Ir(Se-4)(3)]. C6H5CH3 (2), and [K(18-crown-6)(DMF)(2)] [Ir(NCCH3)(2)(Se-4)(2)] (3) (DMF = dimethylformamide) have been prepared from the reaction of [Ir(NCCH3)(2)(COE)(2)][BF4] (COE = cyclooctene) with polyselenide anions in acetonitrile/DMF. Analogous reactions utilizing [Rh(NCCH3)(2)(COE)(2)][BF4] as a Rh source produce homologues of the Ir complexes; these have been characterized by Se-77 NMR spectroscopy. [NH4](3)[Ir(S-6)(3)]. H2O . 0.5CH(3)CH(2)OH (4) has been synthesized from the reaction of IrCl3 . nH(2)O with aqueous (NH4)(2)Sm. In the structure of [K(18-crown-6)](3)[Ir(Se-4)(3)] (1) the Ir(III) center is chelated by three Se-4(2-) Ligands to form a distorted octahedral anion. The structure contains a disordered racemate of the Delta lambda lambda and Lambda lambda lambda conformers. The K+ cations are pulled out of the planes of the crowns and interact with Se atoms of the [Ir(S-4)(3)](3-) anion. [K(2.2.2-cryptand)](3)[Ir(Se-4)(3)]. C6H5CH3 (2) possesses no short K...Se interactions; here the [Ir(Se-4)(3)](3-) anion crystallizes as the Delta lambda delta/Lambda delta lambda racemate. In the crystal structure of [K(18-crown-6)(DMF)(2)][Ir(NCCH3)(2)(Se-4)(2)] (3), the K+ cation is coordinated by an 18-crown-6 ligand and two DMF molecules and the anion comprises an octahedral Ir(III) center bound by two chelating Se-4(2-) chains and two trans acetonitrile groups. The [Ir(Se-4)(3)](3-) and [Rh(Se-4)(3)](3-) anions undergo conformational transformations as a function of temperature, as observed by Se-77 MMR spectroscopy. The thermodynamics of these transformations are: [Ir(Se-4)(3)](3-), Delta H = 2.5(5) kcal mol(-1), Delta S = 11.5(2.2) eu; [Rh(Se-4)(3)](3-), Delta H = 5.2(7) kcal mol(-1), Delta S = 24.7(3.0) eu.

  DOI：

  10.1021/ic960589w
• 作为产物：
  描述：

  selenium 、 18-冠醚-6 、 potassium selenide 、 diμ-chlorotetrakis(η2-cyclooctene)diiridium(I) 、 乙腈 在 AgBF₄ 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 以52%的产率得到[K(18-crown-6)(DMF)2][Ir(acetonitrile)(Se4)2]
  参考文献：
  名称：

  Group 9 Chalcogenometalates

  摘要：

  The compounds [K(18-crown-6)](3)[Ir(Se-4)3] (1), [K(2.2.2-cryptand)](3)[Ir(Se-4)(3)]. C6H5CH3 (2), and [K(18-crown-6)(DMF)(2)] [Ir(NCCH3)(2)(Se-4)(2)] (3) (DMF = dimethylformamide) have been prepared from the reaction of [Ir(NCCH3)(2)(COE)(2)][BF4] (COE = cyclooctene) with polyselenide anions in acetonitrile/DMF. Analogous reactions utilizing [Rh(NCCH3)(2)(COE)(2)][BF4] as a Rh source produce homologues of the Ir complexes; these have been characterized by Se-77 NMR spectroscopy. [NH4](3)[Ir(S-6)(3)]. H2O . 0.5CH(3)CH(2)OH (4) has been synthesized from the reaction of IrCl3 . nH(2)O with aqueous (NH4)(2)Sm. In the structure of [K(18-crown-6)](3)[Ir(Se-4)(3)] (1) the Ir(III) center is chelated by three Se-4(2-) Ligands to form a distorted octahedral anion. The structure contains a disordered racemate of the Delta lambda lambda and Lambda lambda lambda conformers. The K+ cations are pulled out of the planes of the crowns and interact with Se atoms of the [Ir(S-4)(3)](3-) anion. [K(2.2.2-cryptand)](3)[Ir(Se-4)(3)]. C6H5CH3 (2) possesses no short K...Se interactions; here the [Ir(Se-4)(3)](3-) anion crystallizes as the Delta lambda delta/Lambda delta lambda racemate. In the crystal structure of [K(18-crown-6)(DMF)(2)][Ir(NCCH3)(2)(Se-4)(2)] (3), the K+ cation is coordinated by an 18-crown-6 ligand and two DMF molecules and the anion comprises an octahedral Ir(III) center bound by two chelating Se-4(2-) chains and two trans acetonitrile groups. The [Ir(Se-4)(3)](3-) and [Rh(Se-4)(3)](3-) anions undergo conformational transformations as a function of temperature, as observed by Se-77 MMR spectroscopy. The thermodynamics of these transformations are: [Ir(Se-4)(3)](3-), Delta H = 2.5(5) kcal mol(-1), Delta S = 11.5(2.2) eu; [Rh(Se-4)(3)](3-), Delta H = 5.2(7) kcal mol(-1), Delta S = 24.7(3.0) eu.

  DOI：

  10.1021/ic960589w