Influence of the Morphology of Lithiated Copper(I) Sulfides with the Formal Composition “Li₂Cu₄S₃” on Their Stability in Electrochemical Cycling

Abstract

Keywords: Copper / Sulfur / Cluster compounds / Structure elucidation / ElectrochemistryTwo different approaches were developed for the synthesis of lithiated copper(I) sulfide with the formal composition "Li 2 Cu 4 S 3 ". In the first approach, thiolato-bridged copper cluster complexes [Li(dme) 3 ] 2 [Cu 4 (SPh) 6 ] (dme = dimethoxyethane) and [Li(diglyme) 2 ] 2 [Cu 4 (SPh) 6 ] (diglyme = diethylene glycol dimethyl ether) were decomposed/thermolized at 400°C to form the lithiated copper(I) sulfides upon cleavage of the ether ligands and 3 equiv. of SPh 2 . In the second approach, Li 2 S and 2 equiv. of Cu 2 S were allowed to react in quartz ampoules sealed under vacuum at 400°C. The as-synthesized powders reveal complex room-temperature XRD powder patterns with clear differences between the two materials. Scanning electron microscopy reveals that the material synthesized by thermolysis of the cluster material is com-

Halide-bridged tetranuclear organocopper(i) clusters supported by indolyl-based NCN pincer ligands and their catalytic activities towards the hydrophosphination of alkenes

“…This difference reflected in the lack of symmetry in the Cu 4 tetrahedron could probably be ascribed to the different coordination of the Cl atom and indolyl-based NCN pincer ligand triangular pyramids formed from copper ions. The average Cu–Cu distances in each complex were as follows: 1a (2.641 Å), 1b (2.651 Å), 1c (2.653 Å), 2a (2.673 Å), 2b (2.6434 Å) and 2c (2.667 Å); these were all shorter than those previously reported for the tetrahedron of coppers in complexes [Cu 4 @{(Cp′′′Sm(thf)) 4 S 6 }] (2.826 Å), 65 [Ph 4 P] 2 [Cu 4 (SPh) 6 ] (2.760 Å) 66 and [Li(15-crown-5)(thf)] 2 [Cu 4 (SPh) 6 ] (2.730 Å). 67…”

Realgar as a Building Block for Lanthanide Clusters: Encapsulation of a Copper Cluster by a Lanthanide Cluster

“…Alternatively, the endohedral cluster can be described as [Cu 4 @{(Cp‴Sm(thf)) 4 S 6 }], in which a Cu 4 tetrahedron (gray colored polyhedron in Figures and ) is encapsulated by the samarium sulfido cluster {(Cp‴Sm(thf)) 4 S 6 }. The Cu 4 S 6 8– structural motif (Figure ) has been described previously in [Li(15-crown-5)(thf)] 2 [Cu 4 (SPh) 6 ] and [Ph 4 P] 2 [Cu 4 (SPh) 6 ] . The observed Cu–S bond distances (2.240(3)–2.279(3) Å, av.…”

“…2.76 Å) and [Li(15-crown-5)(thf)] 2 [Cu 4 (SPh) 6 ] (av. 2.730 Å). , The outer shell of 5 is a Sm 4 tetrahedron, in which the Sm atoms are capping the faces of the Cu 4 tetrahedron. Each Sm atom binds to three sulfur atoms of the inner Cu 4 S 6 8– subcluster.…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…PhSSiMe3, O2 / THF, 3 h C [155] Please do not adjust margins Please do not adjust margins ) have been extensively studied, and can be obtained by reacting a copper salt with the desired thiolate or by using a monomeric precursor complex already containing the SR species in most cases. [157][158][159][160][161][162][163][164][165][166][167][168][169] In some cases, this involves a reduction of the copper atoms from Cu II to Cu I . Different synthetic approaches have also been showcased.…”

“…CuN(SiMe3)2, LiN(SiMe3)2, HSPh, 15-crown-5 / THF, slight heat, 5 min C [162] [Me4N]2[Cu4(SMe)6] (249)…”