Abstract
Herein, we describe the preparation of heteronuclear dirhodium-silver complexes by reaction between molecular Rh(II)-Rh(II) compounds [Rh2(μ-O2CR)4L2] (R = Me, Ph (1), CH2OEt (2); L = solvent molecules) with paddlewheel structure and PPh4[Ag(CN)2]. One-dimensional coordination polymers of (PPh4)n[Rh2(μ-O2CR)4Ag(CN)2]n (R = Me (3), Ph (4), CH2OEt (5)) formula have been obtained by replacement of the two labile molecules in the axial positions of the paddlewheel structures by a [Ag(CN)2]− bridging unit. The crystal structures of 3–5 display a similar arrangement, having anionic chains with a wavy structure and bulky (PPh4)+ cations placed between the chains. The presence of the (PPh4)+ cations hinders the existence of intermolecular Ag-Ag interactions although several C-H····π interactions have been observed. A similar reaction between [Rh2(μ-O2CCMe3)4(HO2CCMe3)2] and PPh4[Ag(CN)2] led to the molecular compound (PPh4)2{Rh2(μ-O2CCMe3)4[Ag(CN)2]2} (6) by replacement of the axial HO2CCMe3 ligands by two [Ag(CN)2]− units. The trimethylacetate ligand increases the solubility of the complex during the crystallization favouring the formation of discrete heteronuclear species.
Highlights
In the chemistry of compounds with a direct metal-metal bond the dirhodium complexes play a prominent role because their properties span very different fields [1,2,3]
The Rh2 4+ unit presents in the tetracarboxylatodirhodium(II) complexes has been used to achieve a large number of coordination polymers
The branched trimethylacetate ligand, which favours the solubility of the starting dirhodium complex, polymers of which the type (PPh4)nthe
Summary
In the chemistry of compounds with a direct metal-metal bond the dirhodium complexes play a prominent role because their properties span very different fields [1,2,3]. The majority of these compounds contain a diamagnetic Rh2 4+ core with a σ2 π4 δ2 δ*2 π*4 electronic configuration leading to a net metal-metal bond order of one. One-dimensional polymers have been obtained using bridging ligands between the dirhodium units [16,17,18,19]
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