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Syntheses and Structures of Alkaline Earth−Transition Metal Bimetallic Complexes As Heterogeneous Hydrodechlorination Catalyst Precursors

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journal contribution
posted on 2009-01-05, 00:00 authored by Errun Ding, Matthew R. Sturgeon, Aaron Rath, Xuenian Chen, Mark A. Keane, Sheldon G. Shore
A series of alkaline earth−transition metal heterobimetallic complexes {(DMF)xM(μ-CN)yM*(CN)4−y} [M = Ba: M* = Ni 1, M* = Pd 2, M* = Pt 3; M = Sr: M* = Ni 4, M* = Pd 5, M* = Pt 6; x = 3 or 4; y = 3 or 4] was prepared. Single-crystal X-ray diffraction analysis revealed that {(DMF)4Ba(μ-CN)3Ni(CN)} 1, {(DMF)4Sr(μ-CN)3Ni(CN)} 4, {(DMF)4Sr(μ-CN)3Pd(CN)} 5, and {(DMF)4Sr(μ-CN)3Pt(CN)} 6 form isostructural one-dimensional “ladder” arrays through isocyanide linkages (M-NC-M*), while {(DMF)3Ba(μ-CN)4Pd} 2, and {(DMF)3Ba(μ-CN)4Pt} 3 are two-dimensional puckered sheet like arrays. These bimetallic complexes can serve as effective precursors for the synthesis of supported bimetallic catalysts. It has been established that Ba−Pd/SiO2 and Sr−Pd/SiO2 catalysts, prepared from 2 and 5 loaded onto a silica support, delivered specific reaction rates in the hydrodechlorination of mono- and dichloro benzene that were over an order of magnitude greater than that achieved with conventional Pd/SiO2.