Synthesis and properties of palladium diselenolenes: X-ray crystal structures of [Pd[SeC(R(1))=C(R(2))Se](PBu(3))(2)] [R(1), R(2) = (CH(2))(n), n = 4, 5, 6].
The reaction between [Pd(2)(dba)(3)] (dba = dibenzylideneacetone), tributylphosphine, and a bis(cycloalkeno)-1,4-diselenin leads to either a mononuclear diselenolene [Pd[SeC(R(1))=C(R(2))Se](PBu(3))(2)] or a dinuclear diselenolene [Pd(2)[SeC(R(1))=C(R(2))Se](2)(PBu(3))(2)] [R(1), R(2) = (CH(2))(n), n = 4, 5, 6] depending on the stoichiometry employed. Treatment of the dinuclear diselenolenes with 1,2-bis(diphenylphosphino)ethane (dppe) provides a high-yielding route to the mononuclear species [Pd[SeC(R(1))=C(R(2))Se](dppe)]. All new compounds have been characterized by standard spectroscopic and analytical techniques, in particular by multinuclear NMR spectroscopy; the structure of each of the mononuclear tributylphosphine complexes has been determined by X-ray crystallography. Computational studies show that the observed asymmetry of the diselenolenes in the solid state is a result primarily of intramolecular repulsive interactions between the ligands.
Ford
Susan
S
Department of Chemistry, University of Wales Swansea, Singleton Park, Swansea, U.K.
Morley
Christopher P
CP
Di Vaira
Massimo
M