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Metal Vapour Synthesis of an Organometallic Barium(0) Synthon
Oliver P E Townrow1, Christian Färber1, Ulrich Zenneck1
1Inorganic and Organometallic Chemistry, Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058, Erlangen, Germany.
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'')⋅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.
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The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.