Synthesis and Structure of Two Ionic Copper Indium Selenolate Cluster Complexes [As(C₆H₅)₄]₂[Cu₆In₄(SeC₆H₅)₁₆Cl₄] and [As(C₆H₅)₄][Cu₇In₄(SeC₆H₅)₂₀]

Abstract

The reaction of PhSeSiMe3, CuCl, InCl3, and Ph4AsCl in CH2Cl2 results in crystals of the structurally closely related, ionic clusters (AsPh4)2[Cu6In4Cl4(SePh)16] and (AsPh4)[Cu7In4(SePh)20], with product ratios dependent on the initial PhSeSiMe3 concentration. Both molecules display a fused four‐adamantoid structure related to the solid‐state structure of CuInSe2. Since the crystallographic analysis for [Cu7In4(SePh)20]– remained ambiguous with respect to the assignment of one of the copper atoms, we performed a high‐resolution mass spectrometric analysis as well as DFT computations to address this problem. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Synthesis and Structural Characterization of Copper(I) Phenylselenolate Complexes Stabilized by N, N′‐Donor Ligands

“…[1][2][3] This is mostly due to the high interest in controlling the size and shape of cluster compounds generated by binary and ternary coinage metal chalcogenides, which leads to properties being between the semiconducting and metallic phases. [4][5][6] Due to the multidisciplinary importance of metal chalcogenolates in fields like biological chemistry, supramolecular chemistry, and material research, they attract attention not only to chemists, but also to physicists, biochemists, and other researchers, who in some way work with chalcogen compounds. [7][8][9] As part of our interest in the synthesis of chalcogenolato compounds of low-valent metal ions, [10,11] particularly copper(I), we started a study with in situ stabilized "PhSeCu" species for the synthesis of new cluster compounds.…”

“…[1][2][3][4][5][6] The methodology developed for the preparation of such phosphine-coordinated Cu 2 Se clusters can be tailored in order to incorporate chemical functionality onto the surfaces of frameworks. [14] Fenske et al described the synthesis of the polyanionic cluster [pyH] 6 [(CuCl) 9 (μ 3 -SePh) 5 (μ 4 -SePh)] by the treatment of tetracopper(I)phosphonitocavitand with PhSeSiMe 3 in THF at low temperatures. [15] More recently, the same authors included 4,4Ј-bipyridine in a similar synthetic route for the synthesis of the dinuclear complex [Cu 2 (4,4Ј-bpy)].…”

Systematic Access of Ternary Organotetrel‐Copper Chalcogenide Clusters by [PhTE3]3− Anions (T=Si, Sn; E=S, Se)

“…[ 1 , 2 ] Discrete complexes and clusters of such compositions have received a lot of attention in recent times owing to their potential as precursors to said materials, as showcased for CuInE 2 (E=S, Se), a promising semiconductor material for energy conversion in solar cells. [ 3 , 4 , 5 , 6 , 7 ] For this reason, many activities in this direction so far have addressed group 13 compounds, be it as supertetrahedral anions[ 8 , 9 , 10 , 11 , 12 ] or as neutral cages. [ 13 , 14 , 15 , 16 , 17 ] Krautscheid and co‐authors have published a series of investigations on compounds exhibiting organic substituents at the group 13 metal, such as [R 3 PCu) 4 (MeM) 4 E 6 ] (R=organic substituent; M=Ga, In).…”

Synthesis and Characterization of HgII/Se/CuI Multinuclear Compounds from Mercury(II) Bis(p‐aminobenzeneselenolate) – Hg(SeC6H4NH2‐p)2

“…Our research group has a vast experience in the synthesis and characterization of metal chalcogenolate clusters, polymers, and complexes, by exploring the reactivity of M ( EAr ) building blocks – mainly Hg(SePh) 2 , Hg(TePh) 2 and Cd(SePh) 2 – in redistribution reactions . This methodology is a good alternative to the well‐established method used by Fenske, Corrigan and co‐workers, which involves the use of silyl reagents E (SiMe 3 ) 2 and RE SiMe 3 as sources of chalcogenide and chalcogenolate ligands, respectively, for the synthesis of metal chalcogenide and chalcogenolate nanoclusters …”