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

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'')⋅Et2 O]8 . Dissolution in benzene or toluene led to replacement of the Et2 O 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, Ph2 C=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.