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

Abstract

A synthetic route to obtain [p‐H2NC6H4Se]2 (1) in good yield was developed, and the crystal structure of the product was characterized for the first time. The synthesis and structure of the mercury(II) derivative [Hg(SeC6H4NH2)2] (2) was also investigated and is reported herein. The versatile coordination chemistry of [Hg(SeC6H4NH2)2] with halides of the same metal and PCy3 allows the synthesis of [Hg(X)(SeC6H4NH2)(PCy3)] (X = Cl, Br, I) (3–5). The products 1, 3–5 were isolated in crystalline form and characterized by X‐ray structure analysis.

Tricarbonylrhenium(I) Complexes with N‐Heterocyclic Thiones and Selenols

“…Such cleavage reactions are not without precedent and have been applied for the synthesis of cluster compounds of mercury and indium by the reaction of appropriate diselenides with elemental metals. [36,37] A similar cleavage reaction has been described recently with the synthesis of an unusual oxidorhenium(V) complex with elemental selenium and two pyridylselenolato ligands, [ReOSe(Sepy) 3 ], from (Sepy) 2 and [ReOCl 3 (PPh 3 ) 2 ]. [38] In all these examples, however, the reduction of the diselenide can readily be explained, either by the oxidation of the metals or by the formation of elemental selenium.…”

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

“…We have already described a very efficient synthetic pathway to obtain compound Hg(SeC 6 H 4 NH 2 ‐ p ) 2 in a prior publication, but by then, we were not able to obtain single crystals of it. In continuing our studies with this compound we manage to finally obtain a crystalline structure of 1 by dissolving Hg(SeC 6 H 4 NH 2 ‐ p ) 2 in hot 1,4‐dioxane and allowing the solution to cool down to room temperature.…”

“…General: The compounds [ p ‐H 2 NC 6 H 4 Se] 2 and Cu(PPh 3 )Br were prepared according to literature procedures. Other analytical and grade reagents and solvents were obtained commercially (Aldrich or Sigma), and the solvents were freshly distilled before use.…”

“…Although an additional stabilization of the metal selenolate complexes by internal chelate coordination is prevented, we believe that this configuration will allow us to obtain metal selenolates structures with higher nuclearity. By our knowledge, the complexes [Hg(PCy 3 )(SeC 6 H 4 NH 2 ‐ p ) X ] ( X = Cl, Br, I) have been the first published crystalline structures derived from the p ‐aminobenzeneselenolate ligand ([ p ‐H 2 NC 6 H 4 Se] – ) . In this paper, we report the results of our continued studies with this ligand, providing the crystalline structural characterization of [Hg(SeC 6 H 4 NH 2 ) 2 ] 2 · diox ( 1· diox) and its copper(I) derivatives, the new ternary compounds HgCu 2 X 2 (SeC 6 H 4 NH 2 ) 2 (PPh 3 ) 4 · 4diox [ X = Br ( 2· 4diox) and I ( 3· 4diox)].…”

“…Another way to diversify the structures of our compounds is by the use of different organic substituents instead of common phenyl ring substituents. We became interested in the effect of donor amino, alkyl and methoxy groups in the structure and properties of metal aryl‐chalcogenolate compounds …”