Cyclo-[Ni(μ2-SPh)2]9和Cyclo-[Ni(μ2-SPh)2] 11:含有几何上前所未有的9元和11元环体系的新型低聚环型镍(II)硫代酸盐

S. Ivanov, Michael A. Kozee, W. A. Merrill, S. Agarwal, L. F. Dahl
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引用次数: 42

摘要

报道了两种新的低聚型环面镍(II)单硫酸盐环体系,cyclo-[Ni(SPh)2]11(1)和cyclo-[Ni(SPh)2]9(2),它们分别含有迄今未知的11元(n = 11)和9元(n = 9)环的几何形状。我们最初分离到的1是一个意想不到的副产品,它是由于烷基/苯基硫醇与最近制备的纳米结构[Au16Ni24(CO)40]4−簇反应产生纳米结构金硫酸盐簇的失败导致的。由于1的独特结构,我们设计了通过PhSNa与Ni(ClO4)2在THF或DMF中直接合成的方法来制备它。在低温下缓慢加入反应物可得到两种1型晶体:即先前分离的三斜晶(P)和溶剂化的单斜晶(C2/c) (1a)。反应物在室温下的正常混合产生了三角晶体形式(P12/c),确定为环-[Ni(SPh)2]9(2)。1和2的原子排列和化学计量是通过低温CCD区域探测器x射线衍射研究明确建立的;特别值得注意的是,1的两种晶体形式的结构具有几乎相同的分子几何形状(包括苯基环取向)以及封装的四氢呋喃分子。这些新的空气稳定分子加入到环-[Ni(μ2-SR)2]n族(n = 4,5,6和8)中,具有特别的立体化学意义,因为:(1)与以往已知的单齿硫酸盐桥接分子理想地具有规则的凸镍-s环形结构形成鲜明对比的是,在三斜晶型和单斜晶型中的非镍镍1和在三角晶型中的非镍镍2中发现的组装的n局域边缘融合方形平面[NiS4]亚基分别具有不规则形状的混合凹/凸环形伪c2v和伪d3h环几何形状,在几何上是独一无二的;(2) 1是已知的环-[Ni(SR)2]n低聚物中第一个具有共结晶溶剂化客体分子(即THF)的宿主分子;(3)在1和2中观察到的与高度锥体硫原子相连的相邻苯基环的取向表明,存在弱吸引的成对苯基⋯苯基分散力,这些分散力被认为稳定了这些新型的镍(II)苯基硫酸酯低聚物。在假设不存在空间拥挤的r取代基和/或异常填充效应的情况下,对所得到的整个环-[Ni(SPh)2]n族(n = 4,5,6,8,9和11)的理想Ni -s环几何形状的显著固态结构特征进行了比较分析。通过正式插入两个相邻的[Ni(SPh)2]单元,在2中伪三重9元环的不对称扩大,以获得1中11元环的类似Ni - s框架,这归因于客体分子的细长模板几何形状,以及维持吸引的对苯基环相互作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Cyclo-[Ni(μ2-SPh)2]9 and cyclo-[Ni(μ2-SPh)2]11: new oligomeric types of toroidal nickel(II) thiolates containing geometrically unprecedented 9- and 11-membered ring systems
Two new oligomeric types of toroidal nickel(II) monothiolate ring systems, cyclo-[Ni(SPh)2]11 (1) and cyclo-[Ni(SPh)2]9 (2), containing heretofore unknown 11-membered (n = 11) and 9-membered (n = 9) ring-geometries, respectively, are reported. Our initial isolation of 1 was as an unexpected by-product that resulted from unsuccessful attempts to produce crystalline nanostructural gold thiolate clusters from reactions of alkyl/phenyl thiols with the recently prepared nanostructural [Au16Ni24(CO)40]4− cluster. The unique architecture of 1 led to a designed preparation of it by a direct synthetic route involving reactions of PhSNa with Ni(ClO4)2 in THF or DMF. Slow addition of the reactants at low temperature afforded two crystal forms of 1: namely, the previously isolated triclinic crystals (P) as well as solvated monoclinic crystals (C2/c) (1a). Normal mixing of the reactants at room temperature gave rise to a trigonal crystal form (P12/c) that was determined to be cyclo-[Ni(SPh)2]9 (2). The atomic arrangements and stoichiometries of both 1 and 2 were unequivocally established from low-temperature CCD area-detector X-ray diffractometry studies; particularly noteworthy is that the structures of both crystal forms of 1 possess nearly identical molecular geometries (including the phenyl-ring orientations) along with an encapsulated THF molecule. These new air-stable molecular additions to the cyclo-[Ni(μ2-SR)2]n family (with n = 4, 5, 6, and 8) are of particular stereochemical interest in that: (1) in sharp contrast to the previously known monodentate thiolate-bridged members which ideally possess regular convex Ni–S toroids, the assembled n-localized edge-fused square-planar [NiS4] subunits found in the triclinic and monoclinic crystal forms of undecanickel 1 and in the trigonal crystal form of nonanickel 2 have irregularly-shaped mixed concave/convex toroidal pseudo-C2v and pseudo-D3h ring geometries, respectively, that are geometrically unique; (2) 1 is the first host member of any known cyclo-[Ni(SR)2]n oligomer to have a co-crystallized solvated guest molecule (viz., THF); and (3) the observed orientations of adjacent phenyl rings attached to the highly pyramidal sulfur atoms in both 1 and 2 suggest the occurrence of weakly attractive pairwise phenyl⋯phenyl dispersion forces that are presumed to stabilize these novel nickel(II) phenylthiolate oligomers. A comparative analysis of the salient solid-state structural features of the idealized Ni–S ring geometries of the resulting entire cyclo-[Ni(SPh)2]n family (n = 4, 5, 6, 8, 9, and 11) is presented (under the assumed absence of sterically crowded R-substituents and/or abnormal packing effects). The unsymmetrical enlargement of the pseudo-threefold 9-membered ring in 2 by the formal insertion of two adjacent [Ni(SPh)2] units to give an otherwise analogous Ni–S framework of the 11-membered ring in 1 is attributed to the elongated template-geometry of the guest molecule coupled with the maintenance of attractive pairwise phenyl ring interactions.
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