title: Synthesis and characterization of potassium aryl- and alkyl-substituted silylchalcogenolate ligands.
abstract: 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] () and [K(18-crown-6)][SiPh2(t)Bu] (), respectively, as the reaction products in high yield. Compounds and were fully characterized including by multi-nuclear NMR, UV/vis and IR spectroscopies. Addition of elemental chalcogen to either or , results in facile chalcogen insertion into the potassium-silicon bond to afford the silylchalcogenolates, [K(18-crown-6)][E-SiPh2R] (E = S, R = Ph (); E = Se, R = Ph (); E = Te, R = Ph (); E = S, R = (t)Bu (); E = Se, R = (t)Bu (); E = Te, R = (t)Bu ()), in moderate to good yield. The silylchalcogenolates reported herein were characterized by multi-nuclear NMR, UV/vis 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.
authors.affiliation: Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. gaunt@lanl.gov and Chemistry Department, Natural Sciences and Mathematics Division, Transylvania University, Lexington, Kentucky 40508, USA.
authors.forename: Jessie L
authors.initials: JL
authors.lastname: Brown
authors.affiliation: Chemistry Department, Natural Sciences and Mathematics Division, Transylvania University, Lexington, Kentucky 40508, USA.
authors.forename: Ashley C
authors.initials: AC
authors.lastname: Montgomery
authors.affiliation: Chemistry Department, Natural Sciences and Mathematics Division, Transylvania University, Lexington, Kentucky 40508, USA.
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Samaan
authors.affiliation: Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. gaunt@lanl.gov.
authors.forename: Michael T
authors.initials: MT
authors.lastname: Janicke
authors.affiliation: Materials Physics and Applications Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors.forename: Brian L
authors.initials: BL
authors.lastname: Scott
authors.affiliation: Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. gaunt@lanl.gov.
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Gaunt