Coordination Chemistry of Anticrowns. Isolation of
the Chloride Complex of the Four-Mercury Anticrown {[(o,o′‑C6F4C6F4Hg)4]Cl}− from the
Reaction of o,o′‑Dilithiooctafluorobiphenyl
with HgCl2 and Its Transformations to the Free Anticrown
and the Complexes with o‑Xylene, Acetonitrile,
and Acetone
Version 2 2017-06-22, 19:17
Version 1 2017-06-22, 16:03
Posted on 2017-06-22 - 19:17
The paper reports
that the interaction of o,o′-dilithiooctafluorobiphenyl
with HgCl2 in ether results in the formation of the lithium
chloride complex
Li{[(o,o′-C6F4C6F4Hg)4]Cl} (11) of the four-mercury anticrown (o,o′-C6F4C6F4Hg)4 (12) along with the earlier isolated and characterized
three-mercury anticrown (o,o′-C6F4C6F4Hg)3 (2). The complex was identified by the reaction with 12-crown-4
and determination of the structure of the [Li(12-crown-4)2]{[(o,o′-C6F4C6F4Hg)4]Cl} (13) formed. According to an X-ray analysis, the chloride anion in 13 is simultaneously coordinated with all four Hg centers
of the anticrown, forming with them a pyramidal Hg4Cl fragment.
The reaction of 11 (in the form of an acetonitrile solvate, 11·nMeCN) with boiling water leads to
removal of LiCl from 11 and to the formation of free
anticrown 12, the subsequent recrystallization of which
from o-xylene affords the o-xylene
complex {[(o,o′-C6F4C6F4Hg)4](o-Me2C6H4)2} (14). The obtained 14 forms in the crystal infinite chains
consisting of alternating anticrown units and bridging o-xylene moieties. Another o-xylene molecule in each
macrocyclic fragment of the chain plays the role of a terminal ligand.
In both cases, the o-xylene ligands in 14 are bonded to only one Hg center of the corresponding mercuramacrocycle.
The back-conversion of complex 14 into 12 and o-xylene proceeds in the course of its thermal
decomposition under vacuum at 100–120 °C. The reaction
of 12 with acetonitrile yields the nitrile complex {[(o,o′-C6F4C6F4Hg)4](MeCN)2} (15), which also forms infinite polymeric chains in the crystal. In
each monomeric unit of the chain, the corresponding bridging nitrile
is bonded to only one mercury atom of the anticrown moiety, whereas
the other nitrile ligand is coordinated with two Hg sites. The synthesis
and structure of the complex {[(o,o′-C6F4C6F4Hg)4](Me2CO)2(H2O)} (16), containing two acetone and one water ligand per molecule of 12, are also reported. Each acetone molecule in 16 interacts with only one Hg atom of 12, while the water
molecule is coordinated with two mercury centers and, in addition,
forms H-bonds with the oxygen atoms of the acetone species.
CITE THIS COLLECTION
DataCite
3 Biotech
3D Printing in Medicine
3D Research
3D-Printed Materials and Systems
4OR
AAPG Bulletin
AAPS Open
AAPS PharmSciTech
Abhandlungen aus dem Mathematischen Seminar der Universität Hamburg
ABI Technik (German)
Academic Medicine
Academic Pediatrics
Academic Psychiatry
Academic Questions
Academy of Management Discoveries
Academy of Management Journal
Academy of Management Learning and Education
Academy of Management Perspectives
Academy of Management Proceedings
Academy of Management Review
Tugashov, Kirill
I.; Gribanyov, Dmitry A.; Dolgushin, Fedor M.; Smol′yakov, Alexander F.; Peregudov, Alexander S.; Klemenkova, Zinaida S.; et al. (2017). Coordination Chemistry of Anticrowns. Isolation of
the Chloride Complex of the Four-Mercury Anticrown {[(o,o′‑C6F4C6F4Hg)4]Cl}− from the
Reaction of o,o′‑Dilithiooctafluorobiphenyl
with HgCl2 and Its Transformations to the Free Anticrown
and the Complexes with o‑Xylene, Acetonitrile,
and Acetone. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.7b00315
or
Select your citation style and then place your mouse over the citation text to select it.
SHARE
Usage metrics
Read the peer-reviewed publication
AUTHORS (9)
KT
Kirill
I. Tugashov
DG
Dmitry A. Gribanyov
FD
Fedor M. Dolgushin
AS
Alexander F. Smol′yakov
AP
Alexander S. Peregudov
ZK
Zinaida S. Klemenkova
OM
Ol′ga V. Matvienko
IT
Irina A. Tikhonova
VS
Vladimir B. Shur