Copper(i) halide clusters based upon ferrocenylchalcogenoether ligands: donors, halides and semi-rigidity effects on the geometry and catalytic activity

Abstract

Six copper(i) halide clusters based upon ferrocenyltelluroethers or ferrocenylselenoethers, 1-6, have been synthesized and structurally characterized by an X-ray crystallographic study. These structures include a discrete step-cubane Cu4I4 cluster, a 1D chain with rhomboid Cu2X2 clusters, a 1D chain with cubane Cu4I4 clusters and a 2D network with Cu2I2 clusters. 1-3 are the first structurally characterized example of copper(i) clusters with telluroethers. Their different nuclearities and geometries can be attributed to the different donor atoms and chain flexibility in the ligands. The catalytic activities of six clusters were then investigated in the Ullmann C-N cross-coupling reaction and 2 displayed the best performance with a target product N-(4-phenyl)imidazole in 91.3% yield. From the viewpoint of structure, the specific steric acceptance around Cu(i) in 2 may allow imidazole and iodobenzene to stepwise coordinate with the copper center and give the target product effectively.

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

“…Nowadays, the design of new materials focuses on introducing this motif or higher-nuclear derivatives (i.e., Cu x X x L y ; X = Cl, Br, I; x = 2–8; 4 < y < 8) inside 1D, 2D, and 3D coordination polymers through the use of bi- and polydentate ligands. In parallel, the replacement of the N - and P -donor homo-ligands by chalcogenoethers (literature reveals that the S -donor ligands are the most reported) also leads to 1D, 2D, and 3D coordination polymers. − From these networks, a large range of applications have emanated including luminescent sensors; − light emitting diodes; dye sensitized solar cells; , homo- − and heterogeneous , thermo-, electro-, and photocatalysts; and self-healing materials. , Many of these properties stem from the redox-active couple (Cu­(I) → Cu­(II) + 1e – ) and luminescent clusters often designated as secondary building units (SBUs), and a few structure-property relationships have been shown. For instance, the two most encountered SBU motifs are the Cu 4 I 4 L 4 cubane and Cu 2 I 2 L 4 rhomboid (>80% of occurrence), − respectively, belonging to globular and quasi-planar motifs.…”

1,3-Dithianes as Assembling Ligands for the Construction of Copper(I) Coordination Polymers. Investigation of the Impact of the RC(H)S2C3H6 Substituent and Reaction Conditions on the Architecture of the 0D–3D Networks

“…[73][74][75][76][77][78][79][80][81] Coordination polymers based upon ferrocenyltelluroethers or ferrocenylselenoethers are pre-catalysts promoting Ullmann C-N cross-coupling reactions in solution. 82 Reaction of metal ions with ferrocenes functionalized with bis(thioether) substituents can give rise to the formation of discrete clusters. 83,84 Introduction of an additional donor site as in the case of 1,1-(4dipyridinethio)ferrocene led to the formation of 1D CP when reacted with Cu(I) salts.…”

1,3-Dithiolane and 1,3-Ferrocenyl-dithiolane as Assembling Ligands for the Construction of Cu(I) Clusters and Coordination Polymers

“…Due to the chemical stability associated with the electrochemical redox-activity of a ferrocenyl fragment, numerous organometallic polymers bearing a ferrocenyl-unit in the main chain or as pendant side-fragment have been described in the literature [33,34]. We have previously described the synthesis and coordination chemistry of thioetherfunctionalized vinyl-ferrocenes [35].…”