Ding Errun, Sturgeon Matthew R, Rath Aaron, Chen Xuenian, Keane Mark A, Shore Sheldon G
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, USA.
Inorg Chem. 2009 Jan 5;48(1):325-30. doi: 10.1021/ic801912x.
A series of alkaline earth-transition metal heterobimetallic complexes {(DMF)(x)M(mu-CN)(y)M*(CN)(4-y)}(infinity) [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)(4)Ba(mu-CN)(3)Ni(CN)}(infinity) 1, {(DMF)(4)Sr(mu-CN)(3)Ni(CN)}(infinity) 4, {(DMF)(4)Sr(mu-CN)(3)Pd(CN)}(infinity) 5, and {(DMF)(4)Sr(mu-CN)(3)Pt(CN)}(infinity) 6 form isostructural one-dimensional "ladder" arrays through isocyanide linkages (M-NC-M*), while {(DMF)(3)Ba(mu-CN)(4)Pd}(infinity) 2, and {(DMF)(3)Ba(mu-CN)(4)Pt}(infinity) 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/SiO(2) and Sr-Pd/SiO(2) 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/SiO(2).
制备了一系列碱土-过渡金属异双金属配合物{(DMF)(x)M(μ-CN)(y)M*(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或4；y = 3或4]。单晶X射线衍射分析表明，{(DMF)(4)Ba(μ-CN)(3)Ni(CN)}(∞) 1、{(DMF)(4)Sr(μ-CN)(3)Ni(CN)}(∞) 4、{(DMF)(4)Sr(μ-CN)(3)Pd(CN)}(∞) 5和{(DMF)(4)Sr(μ-CN)(3)Pt(CN)}(∞) 6通过异氰化物键合（M-NC-M*）形成同构的一维“梯子”阵列，而{(DMF)(3)Ba(μ-CN)(4)Pd}(∞) 2和{(DMF)(3)Ba(μ-CN)(4)Pt}(∞) 3是二维褶皱片状阵列。这些双金属配合物可作为合成负载型双金属催化剂的有效前体。已经确定，由负载在二氧化硅载体上的2和5制备的Ba-Pd/SiO₂和Sr-Pd/SiO₂催化剂在单氯苯和二氯苯的加氢脱氯反应中提供的特定反应速率比传统Pd/SiO₂实现的反应速率高出一个数量级以上。
