Benzeneselenolates of Mercury(II). Crystal and Molecular Structures of [Hg(SePh)2] and (Bu4N)[Hg(SePh)3]

Abstract

The reaction of dibenzenediselenide, (SePh)2, with mercury in refluxing xylene gives bis(benzeneselenolato)mercury(II), [Hg(SePh)2], in a good yield. (nBu4N)[Hg(SePh)3] is obtained by the reaction of [Hg(SePh)2] with a solution of [SePh]– and (nBu4N)Br in ethanol. The solid state structures of both compounds have been determined by X‐ray diffraction. The mercury atom in [Hg(SePh)2] (space group C2, a = 7.428(2), b = 5.670(1), c = 14.796(4) Å, β = 103.60(1)°) is linearly co‐ordinated by two selenium atoms (Hg–Se = 2.471(2) Å, Se–Hg–Se = 178.0(3)°). Additional weak interactions between the metal and selenium atoms of neighbouring molecules (Hg…Se = 3.4–3.6 Å) associate the [Hg(SePh)2] units to layers. The crystal structure of (nBu4N)[Hg(SePh)3] (space group P21/c, a = 9.741(1), b = 17.334(1), c = 21.785(1) Å, β = 95.27(5)°) consists of discrete complex anions and (nBu4N)+ counter ions. The coordination geometry of mercury is distorted trigonal‐planar with Hg–Se distances ranging between 2.5 and 2.6 Å.

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

“…The crystal structure of compound 2 listed in Scheme could not be obtained; however, the compound appeared to be present as a polymeric structure, similar to that of Hg(SePh) 2 5. The similar reactivities of these compounds supported this hypothesis.…”

“…A fraction of the products 3 and 4 was thought to remain in solution, along with any unreacted starting material and Hg X 2 (PCy 3 ) 2 species. It is also possible that the major product in these reactions comprised clusters of novel compounds (or mixtures of them) similar to those described previously by our group and formed as a result of a reaction between [Hg(SeC 6 H 4 NH 2 ‐ p ) 2 ] and [Hg( X )(SeC 6 H 4 NH 2 ‐ p )] 5–14. The high covalent character of the Hg–I bond in 5 reduced the reactivity and permitted isolation of the product in a better yield.…”

“…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.…”

New metalorgano-chalcogenide compounds based on polymeric frameworks constructed by Se–Hg intermolecular interactions: Preparation, structural characterization, and Raman evaluation

“…However, few articles have reported the synthesis and structural characterization of metal-organochalcogen compounds based on polymeric structures constructed by Hg-Se intermolecular interactions [28,29,36,37]. The compounds described in the present study are representative examples of novel metal-organoselenium polymeric frameworks.…”

Synthesis and X‐ray Structural Characterization of the Polymeric Cluster Compound [Hg3(O2SePh)(SePh)5]n

“…E (SiMe 3 ) 2 and RE (SiMe 3 ) act as a single source of E 2– and RE – , with subsequent elimination of chlorosilane derivatives 5–9. We have already demonstrated the use of M ( E Ph) 2 ( M = Cd, Hg; E = Se, Te) as an efficient delivery source of MER for the synthesis of binary complexes,10–12 polymeric structures,12–16 and clusters compounds 17–19…”