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Gradual solid-state redox-isomerism in the lanthanide series
Ist Teil von
Dalton transactions : an international journal of inorganic chemistry, 2024-05, Vol.53 (2), p.885-8856
Ort / Verlag
England: Royal Society of Chemistry
Erscheinungsjahr
2024
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
Oxidation of [(Ar
BIG
-bian)
2−
Yb
2+
(dme)] (
1
) (Ar
BIG
-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene; dme = 1,2-dimethoxyethane) by 0.5 equivalent of Me
2
NC(S)S-S(S)CNMe
2
in dme at ambient temperature affords a mixture of two products, [(Ar
BIG
-bian)
2−
Yb
3+
{SC(S)NMe
2
}
1−
(dme)] and [(Ar
BIG
-bian)
1−
Yb
2+
{SC(S)NMe
2
}
1−
(dme)], which represent two redox-isomers (
2a
and
2b
, respectively). Their ratio in solution depends on the solvent as well as on the temperature. In the solid state, a decrease of temperature (350 → 100 K) caused an electron transfer from the Yb
2+
ion to the Ar
BIG
-bian radical-anion in isomer
2b
to afford isomer
2a
. Accordingly, the ratio of isomers
2a
and
2b
changes from 1 : 1 (350 K) to 3 : 1 (100 K). In contrast, in the dimer [(dme)(dpp-bian)
1−
Yb
2+
(μ-Cl)
2
Yb
3+
(dpp-bian)
2−
(dme)] (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene), which is the sole example of a lanthanide complex that reveals solid-state redox-isomerism (valence tautomerism) reported so far, the electron transfer from the Yb
2+
ion to the dpp-bian radical-anion takes place at around 150 K and is completed within a temperature interval of
ca
. 7 K.
The dithiocarbamate derivative [(Ar
BIG
-bian)Yb{SC(S)NMe
2
}(dme)] (
2
) exhibits a unique gradual solid-state redox-isomerism that involves a temperature-induced reversible electron transfer between the metal and the ligand.