Solid State NMR Studies of Lead(II) Thiourea Materials

Dybowski, Cecil; Glatfelter, Alicia; Bai, Shi; Hidalgo-Martínez, Diego; Segarra, S.; Perry, Dale L.

doi:10.1557/proc-984-0984-mm07-20

Cited by 1 publication

(1 citation statement)

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“…32 Similar studies of the thiourea and phenanthroline complexes of the lead halides show spans of the order of 600-700 ppm, suggesting a holodirected geometry in those cases. 44,45 The difference between the 207 Pb NMR properties of the two types of lead carboxylate structures (Table 1), whether in the span or the isotropic shift, is primarily the result of the values of differences in δ 11 and δ 22 , the two least shielded components. The values of δ 33 , the most shielded component, are similar for all of the lead carboxylates.…”

Section: Nmr Spectroscopymentioning

confidence: 99%

Coordination geometry of lead carboxylates – spectroscopic and crystallographic evidence

et al. 2015

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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 (13)C and (207)Pb 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 (13)C and (207)Pb 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.

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Section: Nmr Spectroscopymentioning

confidence: 99%