Synthesis and properties of cyclic sandwich compounds

Münzfeld, Luca; Gillhuber, Sebastian; Hauser, Adrian; Lebedkin, Sergei; Hädinger, Pauline; Knöfel, Nicolai D.; Zovko, Christina; Gamer, Michael T.; Weigend, Florian; Kappes, Manfred M.; Roesky, Peter W.

doi:10.1038/s41586-023-06192-4

“…Thus, dodenuclear Mg 12 clusters have been isolated, [40] and most recently even larger cyclic M 18 supersandwiches were crystallised (M = Sr, Sm, Eu). [41] The planarity and bond lengths of the two different symmetry independent Anth'' anions in 1 • Et 2 O (Figure 2) are more similar to the structures of neutral Anth'' or the Anth'' *À radical anion than Anth'' 2À in Mg(Anth'') • (THF) 2 (Figure S24). [27,28,42] This observation should not lead to conclusions on ligand charge, which is closer to À 2 thanÀ 1 (see below), but is related to the large size and low electronegativity of Ba resulting in highly ionic multihapto Ba-Anth'' bonding.…”

mentioning

confidence: 83%

Metal Vapour Synthesis of an Organometallic Barium(0) Synthon

Townrow,

Färber,

Zenneck

et al. 2023

Angew Chem Int Ed

2

0

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A hydrocarbon‐soluble barium anthracene complex was prepared by means of metal vapour synthesis. Reaction of 9,10‐bis(trimethylsilyl)anthracene (Anth′′) with barium vapour gave deep purple Ba(Anth′′) which after extraction with diethyl ether crystallised as the cyclic octamer [Ba(Anth′′)⋅Et2O]8. Dissolution in benzene or toluene led to replacement of the Et2O ligand with a softer arene ligand and isolation of Ba(Anth′′)⋅arene. Diffusion ordered spectroscopy (DOSY NMR ) measurements in benzene‐d6 indicate solution species with a molecular weight that equals a trimeric constitution. Natural population analysis (NPA) assigned charges of +1.70 and −1.70 to Ba and Anth′′, respectively, relating to highly ionic Ba2+/Anth′′2− bonding. Preliminary reactivity studies with air, Ph2C=NPh, or H2 show that the complex reacts as a Ba0 synthon by release of neutral Anth′′. This soluble molecular Ba0/BaII redox synthon provides new routes for the syntheses of barium complexes under mild conditions.

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“…Prerequisites for the self‐assembly of such circular aggregates are a combination of large and small ligands, or formation of a polymeric bent supersandwich both leading to curvature and ring formation. Thus, dodenuclear Mg 12 clusters have been isolated, [40] and most recently even larger cyclic M 18 supersandwiches were crystallised (M=Sr, Sm, Eu) [41] …”

Section: Methodsmentioning

confidence: 99%

Metal Vapour Synthesis of an Organometallic Barium(0) Synthon

Townrow,

Färber,

Zenneck

et al. 2023

Angewandte Chemie

0

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A hydrocarbon‐soluble barium anthracene complex was prepared by means of metal vapour synthesis. Reaction of 9,10‐bis(trimethylsilyl)anthracene (Anth′′) with barium vapour gave deep purple Ba(Anth′′) which after extraction with diethyl ether crystallised as the cyclic octamer [Ba(Anth′′)⋅Et2O]8. Dissolution in benzene or toluene led to replacement of the Et2O ligand with a softer arene ligand and isolation of Ba(Anth′′)⋅arene. Diffusion ordered spectroscopy (DOSY NMR ) measurements in benzene‐d6 indicate solution species with a molecular weight that equals a trimeric constitution. Natural population analysis (NPA) assigned charges of +1.70 and −1.70 to Ba and Anth′′, respectively, relating to highly ionic Ba2+/Anth′′2− bonding. Preliminary reactivity studies with air, Ph2C=NPh, or H2 show that the complex reacts as a Ba0 synthon by release of neutral Anth′′. This soluble molecular Ba0/BaII redox synthon provides new routes for the syntheses of barium complexes under mild conditions.

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“…Die Gruppe um Roesky erhielt die ersten ringförmigen Sandwich-Verbindungen (Cyclocene). 45) ) haben der Kristallstruktur zufolge einen inneren Durchmesser von etwa 17 Å. Theoretische Untersuchungen zeigen, wie wichtig die Dispersions-Wechselwirkungen für die Stabilisierung der Ringstruktur sind.…”

Section: Photochemie Und Photophysikunclassified

Trendbericht Anorganik 2024: Nebengruppen, Bioanorganik und Koordinationschemie

Kreidt,

Werncke

2024

Nachr Chem

0

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Hauptgruppen‐ und Molekülchemie: Die leichteste Metall‐Metall‐Bindung im Bisberyllocen; ein doppeltes Highlight in der Carbenchemie: C zweifach oxidiert mit formal vier Valenzelektronen und Bor‐Flanken für extreme Lewis‐Azidität; außergewöhnliche Liganden ermöglichen, ungewöhnlich reaktive Spezies zu isolieren: ein kristallines Triplett‐Bismutiniden. Nebengruppen, Bioanorganik und Koordinationschemie: Rhodiumnitren, zweifach koordiniertes Ytterbium und lumineszierendes Chrom sowie quadratisch‐planares Cu4S.

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Synthesis and properties of cyclic sandwich compounds

Cited by 33 publications

References 37 publications

Metal Vapour Synthesis of an Organometallic Barium(0) Synthon

Metal Vapour Synthesis of an Organometallic Barium(0) Synthon

Metal Vapour Synthesis of an Organometallic Barium(0) Synthon

Trendbericht Anorganik 2024: Nebengruppen, Bioanorganik und Koordinationschemie

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