title: Phenylselenolate Mercury Alkyl Compounds, PhSeHgMe and PhSeHgEt: Molecular Structures, Protolytic Hg-C Bond Cleavage and Phenylselenolate Exchange.
abstract: The phenylselenolate mercury alkyl compounds, PhSeHgMe and PhSeHgEt, have been structurally characterized by X-ray diffraction, thereby demonstrating that both compounds are monomeric with approximately linear coordination geometries; the mercury centers do, nevertheless, exhibit secondary Hg•••Se intermolecular interactions that serve to increase the coordination number in the solid state. The ethyl derivative, PhSeHgEt, undergoes facile protolytic cleavage of the Hg-C bond to release ethane at room temperature, whereas PhSeHgMe exhibits little reactivity under similar conditions. Interestingly, the cleavage of the Hg-C bond of PhSeHgEt is also more facile than that of the thiolate analogue, PhSHgEt, which demonstrates that coordination by selenium promotes protolytic cleavage of the mercury-carbon bond. The phenylselenolate compounds PhSeHgR (R = Me, Et) also undergo degenerate exchange reactions with, for example, PhSHgR and RHgCl. In each case, the alkyl groups preserve coupling to the199Hg nuclei, thereby indicating that the exchange process involves metathesis of the Hg-SePh/Hg-X groups rather than metathesis of the Hg-R/Hg-R groups.
authors.affiliation: Department of Chemistry, Columbia University, New York New York 10027, USA.
authors.forename: Kevin
authors.initials: K
authors.lastname: Yurkerwich
authors.affiliation: Department of Chemistry, Columbia University, New York New York 10027, USA.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Quinlivan
authors.affiliation: Department of Chemistry, Columbia University, New York New York 10027, USA.
authors.forename: Yi
authors.initials: Y
authors.lastname: Rong
authors.affiliation: Department of Chemistry, Columbia University, New York New York 10027, USA.
authors.forename: Gerard
authors.initials: G
authors.lastname: Parkin
keywords: Mercury; ethyl; methyl; selenolate; thiolate