In an effort to generate triple-decker complexes comprising a {PdCl}moiety in the middle deck, we have explored the reactivity of [(Cp*M){μ-BHE}], - (: M = Co, E = S; : M = Co, E = Se; : M = Rh, E = Se; and : M = Ir, E = Se; Cp* = η-CMe), with [PdCl(COD)] (COD = 1,5-cyclooctadiene). The reactions led to the formation of a series of trinuclear heterometallic triple-decker complexes, [(Cp*M){μ-BHEPd(Cl)}], - (: M = Co, E = S; : M = Co, E = Se; : M = Rh, E = Se; and : M = Ir, E = Se). Formation of the complexes - occurred almost instinctively as a single product with the elimination of the COD ligand. These complexes are examples of novel triple-decker species having a planar bridging palladacycle ligand, in which the Pd metal exists as Pd(II) in an uncommon pseudo-octahedral environment with an elongated M-Pd bonding interaction. The new species, -, have been characterized spectroscopically, and the structures of - were confirmed by single-crystal X-ray diffraction studies. The structure and bonding of these molecules were further analyzed with the help of density functional theory studies that found a strong electron donation from the BE (E = S or Se) fragment of the middle ring to the axial metals, while a weak bonding interaction between group 9 metals and Pd.
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