An α-diiminato germylene family: syntheses, structures, and reactivity towards C-C coupled digermylene and digermylene oxide
The synthesis and reactivity of a rigid α-diiminate ligand supported chlorogermylene 2 were demonstrated. The reaction of 2 with hydride donor K[BH( s Bu) 3 ] yielded a hydride addition product, a five-membered 6π-aromatic germylene 3 . A nonaromatic germylene 4 was produced by dehydrochlorination o...
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2022-06, Vol.51 (22), p.8671-8679 |
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Sprache: | eng |
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Zusammenfassung: | The synthesis and reactivity of a rigid α-diiminate ligand supported chlorogermylene
2
were demonstrated. The reaction of
2
with hydride donor K[BH(
s
Bu)
3
] yielded a hydride addition product, a five-membered 6π-aromatic germylene
3
. A nonaromatic germylene
4
was produced by dehydrochlorination of
2
with KN(Si
t
BuMe
2
)
2
. Halide abstraction with AlCl
3
from
2
afforded a cationic germylene
5
, and the reduction of
2
with potassium led to a C-C coupled digermylene
6
via
a radical coupling pathway. Hydrolysis of
2
in the presence of NHC ((
t
Bu-NCH)
2
C:) gave digermylene oxide
7
. DFT investigations of central Ge
II
-rings in molecules
3-5
provided the details of frontier molecular orbitals. The energy level of the lone pair on the Ge atom in
3
is slightly higher than that in
4
, indicating that
3
is the stronger σ-donor than
4
. Digermylene
6
and its diastereoisomer
6a
feature
trans
-bent and
gauche
-bent configurations along their axially chiral C-C bonds, respectively. The conformational and
cis-trans
isomerism was observed by the isolation of crystal structures
7
and
7a
because of intramolecular steric hindrance.
The synthesis and reactivity of a germylene chloride
2
stabilized by a rigid α-diiminate ligand was systematically explored to afford a new family of germylenes, which bonding nature was revealed by their XRD structures and DFT calculations. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/d2dt00981a |