| 182081-59-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• CAS: 182081-59-0
• 化学式: C₁₀H₅N₆Os
• 分子量: 399.39
• InChiKey: WAIOAKHRAQTTKN-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  吡啶 、 tetrabutylammonium pentacyanonitrosylosmate(II) 在 lithium n-butylamide 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 以96%的产率得到
  参考文献：
  名称：

  Formation of n-Butyldiazoate by Reaction of [M(CN)₅NO]^2- (M = Fe, Ru, Os) with Lithium n-Butylamide

  摘要：

  The reactions of [M(CN)(5)NO](2-) (M = Fe, Ru, Os) with lithium n-butylamide are reported for the first time. Free (E)-n-butyldiazoate was found as the only product arising from the amide. This result and the reinvestigation of the reactions of n-butylamine with [Fe(CN)(5)NO](2-) and [Ru(bpy)(2)(NO)Cl](2+) give a strong indication that diazoates (and/or diazoic acids) are intermediates in the reactions of amines with these nitrosyl complexes.

  DOI：

  10.1021/om011026h

文献信息

• Synthesis and Electronic Structure of Pentacyanoosmate(II) Complexes with N-Heterocyclic Ligands
  作者：Leonardo D. Slep、Luis M. Baraldo、José A. Olabe

  DOI：10.1021/ic960377z

  日期：1996.1.1

  The series of complexes [Os-II(CN)(5)L](n-), with L = pyridine or pyrazine derivatives, were prepared in aqueous solution and, in some cases, as sodium or potassium salts. The main feature in the UV-visible spectra is the appearance of an intense, asymmetric MLCT band, split under spin-orbit coupling. The energies and intensities of the MLCT bands decrease and increase, respectively, with the electron-acceptor ability of L, and strong solvatochromic energy shifts are observed in different organic media. The Os(II) complexes can be oxidized chemically or electrochemically to the Os(III) species; the latter show typical LMCT bands in the visible region, independent of L. The redox potentials for the Os-III,Os-II couples (range 0.6-1.0 V (NHE)), shift positively when L becomes more electron-withdrawing or less basic. Reduction potentials for the bound and free Mepz(+) ligand showed similar values, ca. -0.53 V (NHE), for the three [M(CN)(5)L](n-) complexes, suggesting similar back-bonding abilities of Fe, Ru, and Os toward a given L ligand; this is confirmed by the linear plots with unit slope obtained for the energy of the MLCT bands of the [M(CN)(5)L](n-) complexes (M = Fe, Ru) against the values for the [Os(CN)(5)L](n-) complexes. The IR spectra show intense and weak bands at ca. 2050 and 2100 cm(-1), associated with equatorial and axial cyanide stretchings, respectively. The dissociation rate constant for pyrazine release from the [Os(CN)(5)pz](3-) ion shows a saturation kinetic behavior, typical of dissociative mechanisms found for the iron and ruthenium analog complexes; the specific dissociation rate constant, k(-pz) = 2.0 x 10(-8) s(-1) (25 degrees C, I = 0.5 M), is about 3 and 4 orders of magnitude slower than the values found for [Ru(CN)(5)pz](3-) and [Fe(CN)(5)pz](3-), respectively; this is ascribed mainly to the strong a interaction in the Os-L bond.