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

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Summary

Introduction

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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