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Job/Unit: Z14327 /KAP1 Date: 29-09-14 17:43:54
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z201400327e1.xml
ARTICLE
DOI: 10.1002/zaac.201400327
Synthesis and X-ray Structural Characterization of Di-p-
aminobenzenediselenide [p-H2NC6H4Se]2 and its Mercury(II) Derivatives
Fabrício Bublitz,[a] Melina de Azevedo Mello,[a] Daniele Cocco Durigon,[a]
Bárbara Tirloni,[a] and Ernesto Schulz Lang*[a]
Keywords: p-Aminobenzeneselenolate; Mercury; Selenium
Abstract. A synthetic route to obtain [p-H2NC6H4Se]2 (1) in good
[Hg(SeC6H4NH2)2] with halides of the same metal and PCy3 allows
yield was developed, and the crystal structure of the product was char-
the synthesis of [Hg(X)(SeC6H4NH2)(PCy3)] (X = Cl, Br, I) (3–5). The
acterized for the first time. The synthesis and structure of the products 1, 3–5 were isolated in crystalline form and characterized by
mercury(II) derivative [Hg(SeC6H4NH2)2] (2) was also investigated
X-ray structure analysis.
and is reported herein. The versatile coordination chemistry of
The best route to obtaining examples of this class of com-
pounds would involve the reaction of an alkali metal arylselen-
1 Introduction
Metal chalcogenide (ME) and metal chalcogenolate (MER)
compounds have attracted considerable interest in recent years
due to their potential use in diverse research areas ranging
from biological[1] applications to new materials.[2] The high
nuclearity and, consequently, the quantum confinement effects
observed in cluster compounds may be useful in a variety of
applications in the materials research field, for example, in
low-bandgap semiconductors, photovoltaic cells, or IR detec-
tion devices.[3] An interesting feature of these compounds is
their well-defined size, which enables structural investigations
via single-crystal X-ray diffraction studies that are essential for
understanding their properties.[4]
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 devel-
opment of arylchalcogenolate compounds containing donor
substituents.[15] Arylselenolate species prepared with organic
groups bearing nitrogen donor atoms, [ArSe]– (Ar = aromatic
group containing oxazoline, amine, and imino substituents),
have not been as extensively studied as the phenylselenolate
species. To the best of our knowledge, one of the first exem-
ples of arylselenolates compouns with organic groups bearing
olate [ArSe]– MЈx+ (MЈ = Li, Na, K, Mg) with the desired
x
metal halide. For example, the derivatives [OxSe]2M [M = Zn,
Cd, Hg; Ox = 2-(4,4-dimethyl-2-oxazolinyl)benzene] were
prepared in good yield via the metathesis reactions of MCl2
with a lithium areneselenolate, OxSeLi.[17] Unlike the poly-
meric selenolates generally obtained with group 12 metals,
these complexes are monomeric, and their degree of associa-
tion may be controlled by the internal chelation of the oxazol-
ine ligand.
A tridentate amine-selenolate ligand, 4-tert-butyl-2,6-bis(a-
minomethyl)selenophenol, was used for the synthesis of two
dinuclear nickel amine-selenolate compounds.[18] One of these
compounds comprised a mixed-valent NiIINiIII amine-sele-
nolate complex.
The oxidative addition of the 2-aminobenzenedichalcogen-
ides to the anionic [Ni(CO)(SePh)3]– proved to be a successful
approach to preparing various stereoisomers of the arylchalco-
genolate complexes containing delocalized oxidation levels ac-
ross the nickel ion and ligands.[19]
The first gold complexes of the organoselenolate [2-
(Me2NCH2)C6H4Se]– moiety were prepared by the reaction of
[2-(Me2NCH2)C6H4Se]M (M = Li, K) with gold(phosphine)
complexes.[20] The [AuCl(PR3)] species gave the mononuclear
nitrogen donor atoms is the dimeric complex with a p-amino- gold(I) complexes with monophosphine ligands and the dinu-
benzeneselenolate ligand conecting two gold(I) atoms,
[(AuPPh3)2(SeC6H4NH2-p)]SbF6. Until now, this compound
was also the only one that contains the p-aminobenzenesele-
nolate ligand and was only spectroscopically characterized.[16]
clear species with diphosphine ligands and gold(III) com-
pounds.
The molecular structures of the hypervalent diorganodise-
lenide [2-(Et2NCH2)C6H4]2Se2 and the group 12 metal com-
plexes, [2-(R2NCH2)C6H4Se]2M (R = Me, Et; M = Zn, Cd)
were extensively investigated by Silvestru.[21] The metal com-
plexes were obtained by the reaction of the alkali metal sele-
nolate (MЈ = Li, Na) with MCl2 in a 2:1 molar ratio. The crys-
tal and molecular structures revealed monomeric species stabi-
* Prof. E. Schulz Lang
Fax: +55-55-3220 8031
E-Mail: eslang@ufsm.br
[a] Departamento de Química
Universidade Federal de Santa Maria
97105–900 Santa Maria, RS, Brazil
Z. Anorg. Allg. Chem. 0000, ,(), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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