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Metal Vapour Synthesis of an Organometallic Barium(0) Synthon.

Authors :: Townrow OPE
Färber C
Zenneck U
Harder S
Source :: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jan 25; Vol. 63 (5), pp. e202318428. Date of Electronic Publication: 2023 Dec 22.
Publication Year :: 2024
Abstract: 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'')⋅Et <subscript>2</subscript> O] <subscript>8</subscript> . Dissolution in benzene or toluene led to replacement of the Et <subscript>2</subscript> O ligand with a softer arene ligand and isolation of Ba(Anth'')⋅arene. Diffusion ordered spectroscopy (DOSY NMR ) measurements in benzene-d <subscript>6</subscript> 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 Ba <superscript>2+</superscript> /Anth'' <superscript>2-</superscript> bonding. Preliminary reactivity studies with air, Ph <subscript>2</subscript> C=NPh, or H <subscript>2</subscript> show that the complex reacts as a Ba <superscript>0</superscript> synthon by release of neutral Anth''. This soluble molecular Ba <superscript>0</superscript> /Ba <superscript>II</superscript> redox synthon provides new routes for the syntheses of barium complexes under mild conditions.<br /> (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)