Syntheses and Structures of New Tellurium−Mercury Clusters with Twelve- and Six-Membered Rings

Abstract

Clusters with polycyclic twelve-membered rings were formed exclusively from the reaction of [Hg(TePh) 2 ] with HgX 2 in pyridine. Clusters with just six members were formed from the same reaction in DMSO. In both cases, the Mercury chalcogenide compounds have found considerable use in industry, especially as low band gap semiconductors, in photovoltaic applications, and IR detection devices. [1] The synthesis and structural characterization of metal chalcogenide molecules with a defined size and structure provide an interesting approach to this class of materials. [2] Coordination compounds can be adequate precursors because the structure and properties of the resulting material can be modified by the synthesis conditions or the nature and properties of the ligands. Diorganochalcogenide compounds, REϪER (E ϭ S, Se, Te), could be optimal ligands, because they react with mercury under mild conditions to yield [Hg(ER) 2 ] complexes. Although they eventually form polymeric structures by weak intermolecular Hg···E interactions, [3,4] the sulfide and selenide derivatives react with equimolar amounts of HgCl 2 in pyridine to yield metallacyclic compounds [Hg 4 Cl 4 (µ-ER) 4 (py) n ] (E ϭ S, R ϭ tBu, n ϭ 2; [5] E ϭ Se, R ϭ Et, n ϭ 4; E ϭ Se, R ϭ tBu, n ϭ 4. [3] ) The different stoichiometry of the compounds appears to depend on the steric hindrance between pyridine and organic substituent R. Surprisingly, analogous tellurium derivatives have not been reported until now. As part of our interest in organotelluride chemistry, [6] we have investigated the reaction of [Hg(TePh) 2 ] [7] with HgBr 2 in coordinating solvents, in which only the first is soluble.The solid isolated from the reaction mixture could be fully characterized as the cluster [Hg 6 (µ-Br 2 )Br 2 (µ-TePh) 8 (py) 2 ] (1) by single-crystal X-ray diffraction [8] (Figure 1). The structure of 1 exemplifies a rare multinuclear [a] 331 solvent was coordinated to the clusters. The clusters, [Hg 6 (µ-Br) 2 Br 2 (µ-TePh) 8 (py) 2 ] and [Hg 3 X 3 (µ-TePh) 3 ]·2DMSO (X = Cl, Br, I), were characterized by single-crystal X-ray crystallography.compound. The molecule can be considered as being formed from two six-membered Hg 3 (µϪTePh) 3 rings that are bridged by two (µ-TePh) ligands. Additionally, a bromine atom asymmetrically bridges the two mercury atoms in each ring [Hg (1)ϪBr (8) 2.941(2), Hg(3)ϪBr(8) 2.845(2) Å ]. A terminal bromine atom coordinates to the third mercury atom at a shorter distance [Hg(2)ϪBr(9) 2.641(2) Å ].Figure 1. Structure of 1 (with H atoms omitted and each carbon atom represented by a conventional radius for clarity); selected bond lengths [Å ]:

Cadmium bis(phenylselenolate) as a precursor for the synthesis of polymeric Cd(μ-Se)clusters: Crystal and molecular structures of [Cd4(SePh)7(PPh3)X] (X = Cl, Br)

“…Symmetry transformations used to generate equivalent atoms: ( 0 ) 0.5Àx, 0.5 + y, 0.5Àz; ( 00 ) 0.5Àx, 0.5 + y, 0.5Àz. In this work, we have extended the use of Hg(EPh) 2 (E = Se, Te) [4][5][6][7][8][9][10][11] as a precursor for the preparation of clusters to Cd(SePh) 2 , offering a complementary methodology in the place of silyl reagents [15][16][17][18][19][20]. Because this approach should be extensible to the synthons of the general formula M(ER) n for which a great many examples have been reported [21,22], we predict that a systematic methodology for the synthesis of binary and ternary clusters would be possible.…”

“…As part of our interest in organochalcogenide chemistry, we previously investigated the use of Hg(EPh) 2 (E = Se, Te) as a precursor for the preparation of nanoclusters using redistribution reactions [4][5][6][7][8][9][10][11]. The precursor Cd(SePh) 2 can be used in similar reactions to offer a facile route to yield Cd-Se clusters via a ''bottom up" strategy.…”

Synthesis and crystal structure of chalcogenide cluster compound

“…(13), are obtained. 25 When the cluster 3 was re-dissolved in dmso, only the cluster 6 could be isolated. These results suggest that a dynamic process involving the coordination and loss of the solvent is present.…”

“…22,23 We have already reported results about the influence of ligands, coordinating solvents and reaction stoichiometry on the size and stereochemistry of different cluster compounds. [24][25][26][27][28][29][30] In a recent communication we described the reactions of Hg(TePh) 2 [31][32][33] These papers discuss new synthetic routes to achieve either binary as ternary cluster compounds.…”

Synthesis and X‐ray Structural Characterization of Di‐p‐aminobenzenediselenide [p‐H2NC6H4Se]2 and its Mercury(II) Derivatives

“…In recent years, we have extensively explored the synthesis of M (μ‐ E ‐Ph) building blocks and cluster compounds ( E = Se, Te; M = Cd, Hg, Ag, Cu) in an effort to control the reaction conditions that determine the size and shape of the resulting compounds 5–14. We recently turned our attention to the development of arylchalcogenolate compounds containing donor substituents 15.…”