Zinc, Cadmium, and Mercury Complexes with Fluorinated Selenolate Ligands

Abstract

Reductive cleavage of C(6)F(5)SeSeC(6)F(5) with elemental M (M = Zn, Cd, and Hg) in pyridine results in the formation of (py)(2)Zn(SeC(6)F(5))(2), (py)(2)Cd(SeC(6)F(5))(2), and Hg(SeC(6)F(5))(2). Structural characterization of the Zn and Cd compounds reveals tetrahedral coordination environments, while the Hg compound shows a complicated series of linear structures with two short, nearly linear Hg-Se bonds, up to two longer and perpendicular Hg...Se interactions, and no coordinated pyridine ligands. All three compounds exhibit well-defined intermolecular pi-pi-stacking interactions in the solid state. They are volatile and decompose at elevated temperatures to give MSe and either (SeC(6)F(5))(2) or Se(C(6)F(5))(2).

Phenylselenolate mercury alkyl compounds, PhSeHgMe and PhSeHgEt: Molecular structures, protolytic Hg–C bond cleavage and phenylselenolate exchange

“…For additional comparison, these Hg–SeAr bond lengths are similar to those in the two-coordinate homoleptic derivative, Hg(SePh) 2 [2.4802(2) Å], 28 and the four-coordinate complex, [Tm Bu t ]HgSePh [2.5244(4) Å]. 29 It is, nevertheless, appropriate to point out that significantly longer Hg–Se bond lengths have been reported for compounds that feature Hg←Se dative covalent L-type interactions.…”

2-Seleno-1-alkylbenzimidazoles and their diselenides: Synthesis and structural characterization of a 2-seleno-1-methylbenzimidazole complex of mercury

“…34 The Hg–Se bonds in [H(sebenzim Me )] 2 HgCl 2 are, nevertheless, distinctly longer than those in compounds such as the phenylselenolate derivative, Hg(SePh) 2 [2.4802(2) Å]. 35 This difference undoubtedly reflects the fact that H(sebenzim Me ) is an L-type donor and coordinates via a dative bond, whereas PhSe is an X-type ligand and coordinates via a normal covalent bond. 34 The distinction between normal covalent and dative covalent bonds has been highlighted by Haaland, with the lengths of dative bonds being very sensitive to the environment of the acceptor atom.…”

Proton reduction by a bimetallic zinc selenolate electrocatalyst

“…2DMSO reveals the average bond distance of 2.44 (7) Å between Zn and Se and is comparable with the previously reported Se1-Zn1 bond distances, which are in the range of 2.313(3)-2.463( 6) Å (Table 2). [31][32][33][34][35][36][37] The average Zn1-N1 bond distance is 2.199(3) Å, equivalent to those reported for zinc and typical N-donor ligands, which generally range from 2.04 to 2.14 Å (Table 2).…”

“…It is worth noting that, despite several reports on the structurally characterized mercury selenolate complexes, limited examples of structurally characterized zinc selenolates are available. [31][32][33][34][35][36][37][38] Herein, suitably positioned nitrogen and oxygen donor atoms in the ligand presumably stabilized bimetallic zinc core. Characterization of zinc and mercury selenolate complexes 1 and 4 by 77 Se NMR, which is a very sensitive technique towards the electronic environment around the selenium nucleus, revealed signicantly downeld shi (d ¼ À85 and 76 ppm, respectively) as compared to the diselenide 3 (d ¼ 400 ppm).…”