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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Coordination geometry of lead carboxylates - spectroscopic and crystallographic evidence
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Coordination geometry of lead carboxylates - spectroscopic and crystallographic evidence

机译：羧酸铅的配位几何-光谱和晶体学证据

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Despite their versatility, only a few single-crystal X-ray structures of lead carboxylates exist, due to difficulties with solubility. In particular, the structures of long-chain metal carboxylates have not been reported. The lone electron pair in Pb(II) can be stereochemically active or inactive, leading to two types of coordination geometries commonly referred to as hemidirected and holodirected structures, respectively. We report C-13 and Pb-207 solid-state NMR and infrared spectra for a series of lead carboxylates, ranging from lead hexanoate (C6) to lead hexadecanoate (C18). The lead carboxylates based on consistent NMR parameters can be divided in two groups, shorter-chain (C6, C7, and C8) and longer-chain (C9, C10, C11, C12, C14, C16, and C18) carboxylates. This dichotomy suggests two modes of packing in these solids, one for the short-chain lead carboxylates and one for long-chain lead carboxylates. The consistency of the 13C and 207Pb NMR parameters, as well as the IR data, in each group suggests that each motif represents a structure characteristic of each subgroup. We also report the single-crystal X-ray diffraction structure of lead nonanoate (C9), the first single-crystal structure to have been reported for the longer-chain subgroup. Taken together the evidence suggests that the coordination geometry of C6-C8 lead carboxylates is hemidirected, and that of C9-C14, C16 and C18 lead carboxylates is holodirected.
机译：尽管它们具有通用性，但由于溶解度困难，仅存在少量的羧酸铅单晶X射线结构。特别地，尚未报道长链金属羧酸盐的结构。 Pb（II）中的孤电子对可以是立体化学活性的，也可以是无活性的，从而导致两种类型的配位几何结构分别分别称为半定向和全定向结构。我们报告了一系列的羧酸铅，从己酸铅（C6）到十六烷酸铅（C18）的C-13和Pb-207固态NMR和红外光谱。基于一致的NMR参数的羧酸铅可以分为两类：短链（C6，C7和C8）和长链（C9，C10，C11，C12，C14，C16和C18）。这种二分法表明在这些固体中有两种填充方式，一种是短链羧酸铅，另一种是长链羧酸铅。每组中13C和207Pb NMR参数的一致性以及IR数据表明，每个基序代表每个子组的结构特征。我们还报告了壬酸铅（C9）的单晶X射线衍射结构，这是第一个针对长链亚组的单晶结构。综合考虑，证据表明C6-C8羧酸铅的配位几何是半定向的，而C9-C14，C16和C18羧酸铅的配位几何是全定向的。

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