title: Dicoordinate copper(I) silanechalcogenolates.
abstract: The copper silanechalcogenolates tBu3PCuESiPh3 (1, E = O; 2, E = S; 3, E = Se) were prepared from the reaction of [tBu3PCu(CH3CN)3]BF4 with [Ph3SiELi(THF)2]2 in acetonitrile. The compounds were obtained as colorless, crystalline, but thermally labile solids. X-ray crystallography shows that complexes 1-3 are monomeric in the solid state with no Cu...Cu interactions. The Cu atoms have either a linear or a near-linear coordination geometry in all three complexes. Interestingly, the O atom in complex 1 is also linear, which is in contrast to the highly bent S (2) and Se analogues (3). Density functional theory calculations suggest that both the linear geometry of 1 and an associated extremely short Cu-O distance [1.769(4) A] are not the result of pi delocalization but are the result of a fine balance of electrostatic interaction and Pauli repulsion.
authors.affiliation: Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.
authors.forename: Iliana
authors.initials: I
authors.lastname: Medina
authors.forename: Heiko
authors.initials: H
authors.lastname: Jacobsen
authors.forename: Joel T
authors.initials: JT
authors.lastname: Mague
authors.forename: Mark J
authors.initials: MJ
authors.lastname: Fink
mesh_terms: D018011:Chalcogens / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*
chemical_list: D018011:Chalcogens; D009942:Organometallic Compounds; D012821:Silanes; D003300:Copper