Synthesis and Characterization of Potassium Aryl- and Alkyl-Substituted Silylchalcogenolate Salts

Brown, Jessica Lynn; Montgomery, Ashley C.; Samaan, Christopher A.; Janicke, Michael Timothy; Scott, Brian Lindley; Gaunt, Andrew James

doi:10.1039/C5DT04433B

Synthesis and Characterization of Potassium Aryl- and Alkyl-Substituted Silylchalcogenolate Salts

Journal Article · Tue Feb 23 00:00:00 EST 2016 · Dalton Transactions

DOI:https://doi.org/10.1039/C5DT04433B· OSTI ID:1335624

Brown, Jessica Lynn ^[1]; Montgomery, Ashley C. ^[2]; Samaan, Christopher A. ^[2]; Janicke, Michael Timothy ^[3]; Scott, Brian Lindley ^[3]; Gaunt, Andrew James ^[3]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Transylvania Univ., Lexington, KY (United States)
Transylvania Univ., Lexington, KY (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Treatment of either triphenyl(chloro)silane or tert-butyldiphenyl(chloro)silane with potassium metal in THF, followed by addition of 18-crown-6, affords [K(18-crown-6)][SiPh₃] (1) and [K(18-crown-6)][SiPh₂ ^tBu] (2), respectively, as the reaction products in high yield. Compounds 1 and 2 were fully characterized including by multi-nuclear NMR and IR spectroscopies. Addition of elemental chalcogen to either 1 or 2, results in facile chalcogen insertion into the potassium-silicon bond to afford the silylchalcogenolates, [K(18-crown-6)][E– SiPh2R] (E = S, R = Ph (3); Se, R = Ph (4); E = Te, R = Ph (5); E = S, R = ^tBu (6); E = Se, R = ^tBu (7); E = Te, R = ^tBu (8)), in moderate to good yield. The silylchalcogenolates reported herein were characterized by multi-nuclear NMR and IR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the reported compounds crystallize as discrete monomers in the solid-state, a structural feature not previously observed in silylchalcogenolates, providing well-defined access routes into systematic metal complexation studies.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1335624

Report Number(s):: LA--UR-15-28775

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 24 Vol. 45; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Synthesis and Characterization of Potassium Aryl- and Alkyl-Substituted Silylchalcogenolate Salts

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