Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

A homoleptic AgIII complex stabilized by succinimidate ligands

Larsen, Emil Mickey Hilligsøe ; Brock-Nannestad, Theis ; Skibsted, Jørgen ; Reinholdt, Anders LU and Bendix, Jesper (2024) In Chemical Science 15(43). p.18067-18075
Abstract

Herein, the first example of a homoleptic AgIII complex stabilized by a monodentate N-donor ligand is presented. Na2[S2O8] oxidizes the linear AgI complex, Na[Ag(succ)2] (1Na), to form a square planar argentate(III) ion, [Ag(succ)4]–, which crystallizes with a polymeric chain-structure, M[Ag(succ)4] (2M), when treated with alkali metal sulfate M2SO4 (M = K, Rb, Cs). A mixed-valent Robin-Day class I system, [(H2O)Ag][Ag(succ)4] (2Ag), forms in the absence of K+/Rb+/Cs+ ion. Diamagnetic 2Cs displays a succinimide C]O... (More)

Herein, the first example of a homoleptic AgIII complex stabilized by a monodentate N-donor ligand is presented. Na2[S2O8] oxidizes the linear AgI complex, Na[Ag(succ)2] (1Na), to form a square planar argentate(III) ion, [Ag(succ)4]–, which crystallizes with a polymeric chain-structure, M[Ag(succ)4] (2M), when treated with alkali metal sulfate M2SO4 (M = K, Rb, Cs). A mixed-valent Robin-Day class I system, [(H2O)Ag][Ag(succ)4] (2Ag), forms in the absence of K+/Rb+/Cs+ ion. Diamagnetic 2Cs displays a succinimide C]O stretching frequency at higher energy than does the isoelectronic PdII complex, [(H2O)Na]2[Pd(succ)4] (3Na). Moreover, 2Cs displays UV-vis absorptions that are more intense and occur at lower energy than those in 3Na. The electron-deficient nature of 2Cs is further evident from its ability to oxidize water to O2. From109Ag magic-angle spinning NMR studies, a highly deshielded AgIII environment in 2Cs (2080 ppm) relative to the AgI starting material 1Na (492 ppm) is observed.

(Less)
Please use this url to cite or link to this publication:
author
; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemical Science
volume
15
issue
43
pages
9 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85206483104
  • pmid:39416294
ISSN
2041-6520
DOI
10.1039/d4sc04843a
language
English
LU publication?
yes
id
82b89712-fc12-4df2-a62e-cf540812af76
date added to LUP
2024-12-18 15:06:32
date last changed
2025-07-17 08:14:29
@article{82b89712-fc12-4df2-a62e-cf540812af76,
  abstract     = {{<p>Herein, the first example of a homoleptic Ag<sup>III</sup> complex stabilized by a monodentate N-donor ligand is presented. Na<sub>2</sub>[S<sub>2</sub>O<sub>8</sub>] oxidizes the linear Ag<sup>I</sup> complex, Na[Ag(succ)<sub>2</sub>] (1<sup>Na</sup>), to form a square planar argentate(III) ion, [Ag(succ)<sub>4</sub>]<sup>–</sup>, which crystallizes with a polymeric chain-structure, M[Ag(succ)<sub>4</sub>] (2<sup>M</sup>), when treated with alkali metal sulfate M<sub>2</sub>SO<sub>4</sub> (M = K, Rb, Cs). A mixed-valent Robin-Day class I system, [(H<sub>2</sub>O)Ag][Ag(succ)<sub>4</sub>] (2<sup>Ag</sup>), forms in the absence of K<sup>+</sup>/Rb<sup>+</sup>/Cs<sup>+</sup> ion. Diamagnetic 2<sup>Cs</sup> displays a succinimide C]O stretching frequency at higher energy than does the isoelectronic Pd<sup>II</sup> complex, [(H<sub>2</sub>O)Na]<sub>2</sub>[Pd(succ)<sub>4</sub>] (3<sup>Na</sup>). Moreover, 2<sup>Cs</sup> displays UV-vis absorptions that are more intense and occur at lower energy than those in 3<sup>Na</sup>. The electron-deficient nature of 2<sup>Cs</sup> is further evident from its ability to oxidize water to O<sub>2</sub>. From<sup>109</sup>Ag magic-angle spinning NMR studies, a highly deshielded Ag<sup>III</sup> environment in 2<sup>Cs</sup> (2080 ppm) relative to the Ag<sup>I</sup> starting material 1<sup>Na</sup> (492 ppm) is observed.</p>}},
  author       = {{Larsen, Emil Mickey Hilligsøe and Brock-Nannestad, Theis and Skibsted, Jørgen and Reinholdt, Anders and Bendix, Jesper}},
  issn         = {{2041-6520}},
  language     = {{eng}},
  number       = {{43}},
  pages        = {{18067--18075}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Chemical Science}},
  title        = {{A homoleptic Ag<sup>III</sup> complex stabilized by succinimidate ligands}},
  url          = {{http://dx.doi.org/10.1039/d4sc04843a}},
  doi          = {{10.1039/d4sc04843a}},
  volume       = {{15}},
  year         = {{2024}},
}