Crystal Structure of cis-Bis(2,2′-bipyridyl)bis(trifluoromethanesulfonato)cobalt(II)

IF 0.1 Q4 CRYSTALLOGRAPHY
Mari Toyama, Yuichi Yamamoto
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引用次数: 1

Abstract

Cobalt(II) complexes with polypyridyl ligands were used as photo-catalysts for hydrogen generation from water,1 sensitizers in dye-sensitized solar cells,2 or building blocks for magnetic supramoleculars,3 because of their redox and magnetic properties. When synthesizing a new functional cobalt(II) complex with polypyridyl ligands, such as cis-[Co(L)2(N-N)2] or cis-[Co(L-L)(N-N)2] (L = monodentate ligand, L-L = bidentate ligand, N-N = 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) etc.), cis-[Co(solvent)2(N-N)2] or cis-[CoII(OTf )2(N-N)2] (OTf– = trifluoromethanesulfonato or CF3SO3) have been utilized as a precursor.3 This is a popular synthetic method for not only cobalt(II) complexes, but also many transition metal complexes. However, there are only four reports concerning the crystal structure of cis-[MII(OTf )2(bpy)2] (M = Mn, Ni, Cu, or Zn),3 because OTf– ligands might be too labile to be isolated from a reaction solution as single crystals. Smith and co-workers prepared cis-[MII(OTf )2(bpy)2] (M = Mn or Co) complexes from the reaction of cis-[MCl2(bpy)2] with Ag(OTf ) in acetonitrile.3 The cis-[MnII(OTf )2(bpy)2] complex was characterized by elemental analysis, IR spectra, and X-ray crystal structure, whereas the Co(II) complex was reported based on only IR spectroscopic data. Fortunately, we were able to determine the crystal structure of cis-[CoII(OTf )2(bpy)2] (Fig. 1). Here we report on it, and compare the lattice parameters of our Co2+ complex with those of other transition metal complexes, cis-[MII(OTf )2(bpy)2]. We obtained yellow crystals of cis-[CoII(OTf )2(bpy)2], which were suitable for X-ray crystallography, from the reaction mixture of [Co(CO)3(bpy)2](OTf )4 and di-2-pyridylamine (Hdpa) in EtOH–H2O containing a small amount of HOTf(aq). We expected that [Co(bpy)2(Hdpa)] would be obtained from the reaction, but the anticipated complex was not yielded. The 1H NMR spectrum of the product showed that [Co(bpy)3] and a CoIII-Hdpa complex, probably [Co(Hdpa)3] or trans[Co(OH2)2(Hdpa)2], existed in the NMR sample. We tried to crystalize the CoIII-Hdpa complex by the vapor diffusion of diethyl ether into an EtOH–MeOH (1:1) solution of the mixed product. However, this plan went wrong. From the solution, two kinds of yellow crystals, which had different shapes, for [Co(bpy)3](OTf )3 and cis-[CoII(OTf )2(bpy)2], and a yellowbrown oily product, which would be the CoIII-Hdpa complex, were obtained. The Co2+ complex, cis-[CoII(OTf )2(bpy)2], might be produced from a reduction reaction of the Co3+ complex, [Co(CO3)(bpy)2], by EtOH in the reaction solution. We thought that it would be important for coordination chemists, because it is the first report concerning the crystal structure of cis-[CoII(OTf )2(bpy)2]. In 2013, Kurahashi and Fujii reported on a very unique cobalt complex with a salen ligand (Fig. S1, Supporting Information) and an OTf– ligand, [Co(salen)(OTf )], which was characterized by X-ray crystallography, cyclic voltammetry, L-edge X-ray absorption spectroscopy, the temperature dependence of the magnetic moment, X-band EPR spectra, and NMR spectra.5 Based on their experiments, they concluded that the complex contained both [CoIII(salen)(OTf )] and [CoII(salen•+)(OTf )] (salen•+ = salen ligand radical) character, and in the crystal the complex had a significant [CoIII(salen)(OTf )] character compared with the [CoII(salen•+)(OTf )] character.5 This interesting and uncommon complex had been the only reported instance of the Co complex with an OTf– ligand, until our report concerning the common Co2+ complex, cis-[CoII(OTf )2(bpy)2]. X-ray crystallography was performed at 173 K on a Rigaku XtaLAB P200 diffractometer using multi-layer mirror monochromated Cu-Kα radiation. The structure was solved by 2019 © The Japan Society for Analytical Chemistry
顺式双(2,2′-联吡啶基)双(三氟甲烷磺酸)钴(II)的晶体结构
钴(II)配合物与多吡啶基配体被用作水制氢的光催化剂,1染料敏化太阳能电池的敏化剂,2或磁性超分子的构建块,3因为它们的氧化还原和磁性。在用多吡啶配体如顺式-[Co(L)2(N-N)2]或顺式-[Co(L-L)(N-N)2] (L =单齿配体,L-L =双齿配体,N-N = 2,2 ' -联吡啶(bpy)或1,10-菲罗啉(phen)等)合成新的功能钴(II)配合物时,已利用顺式-[Co(溶剂)2(N-N)2]或顺式-[CoII(OTf)2(N-N)2] (OTf - =三氟甲烷磺酸或CF3SO3)作为前驱体这不仅是钴(II)配合物的常用合成方法,也是许多过渡金属配合物的常用合成方法。然而,关于顺式-[MII(OTf)2(bpy)2] (M = Mn, Ni, Cu或Zn)的晶体结构只有四篇报道,3因为OTf -配体可能太不稳定,无法从反应溶液中作为单晶分离出来。Smith等在乙腈中由顺式-[MCl2(bpy)2]与Ag(OTf)反应制备出顺式-[MII(OTf)2(bpy)2] (M = Mn或Co)配合物顺式-[MnII(OTf)2(bpy)2]配合物通过元素分析、红外光谱和x射线晶体结构进行了表征,而Co(II)配合物仅通过红外光谱数据进行了表征。幸运的是,我们能够确定顺式-[CoII(OTf)2(bpy)2]的晶体结构(图1)。在这里,我们报告了它,并将我们的Co2+配合物的晶格参数与其他过渡金属配合物cis-[MII(OTf)2(bpy)2]的晶格参数进行了比较。在含有少量HOTf(aq)的EtOH-H2O中,将[Co(Co)3(bpy)2](OTf)4与二-2-吡啶胺(Hdpa)混合反应,得到了适合x射线晶体学的顺式-[CoII(OTf)2(bpy)2]的黄色晶体。我们期望从反应中得到[Co(bpy)2(Hdpa)],但期望的配合物没有得到。产物的1H NMR谱显示,样品中存在[Co(bpy)3]和CoIII-Hdpa配合物,可能为[Co(Hdpa)3]或反式[Co(OH2)2(Hdpa)2]。我们试图通过乙醚的蒸汽扩散到混合产物的乙氧甲烷(1:1)溶液中来结晶CoIII-Hdpa配合物。然而,这个计划出了问题。从该溶液中,得到了两种不同形状的黄色晶体[Co(bpy)3](OTf)3和顺式-[CoII(OTf)2(bpy)2],以及一种黄褐色的油产物,即CoIII-Hdpa配合物。Co2+络合物cis-[CoII(OTf)2(bpy)2]可能是由Co3+络合物[Co(Co3)(bpy)2]在反应溶液中被EtOH还原而产生的。我们认为这对配位化学家来说很重要,因为这是关于顺式-[CoII(OTf)2(bpy)2]晶体结构的第一篇报道。2013年,Kurahashi和Fujii报道了一种非常独特的钴配合物,它具有salen配体(图S1,辅助信息)和OTf -配体[Co(salen)(OTf)],并通过x射线晶体学、循环伏安法、l边x射线吸收光谱、磁矩的温度依赖性、x波段EPR光谱和核磁共振光谱进行了表征根据他们的实验,他们得出配合物同时含有[CoIII(salen)(OTf)]和[CoII(salen•+)(OTf)] (salen•+ = salen配体自由基)特征,并且在晶体中与[CoII(salen•+)(OTf)]特征相比,配合物具有显著的[CoIII(salen)(OTf)]特征在我们报道常见的Co +配合物cis-[CoII(OTf)2(bpy)2]之前,这个有趣而不常见的配合物一直是唯一报道的Co配合物与OTf -配体的例子。在Rigaku XtaLAB P200衍射仪上使用多层镜面单铬化Cu-Kα辐射在173 K下进行x射线晶体学研究。该结构是在2019年解决的©日本分析化学学会
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CiteScore
0.60
自引率
50.00%
发文量
17
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