Terminal dysprosium and holmium organoimides
Terminal rare-earth-metal imide complexes Tp t Bu,Me Ln(NC 6 H 3 iPr 2 -2,6)(dmap) of the mid-late rare-earth elements dysprosium and holmium were synthesized via double methane elimination of Lewis acid stabilized dialkyl precursors Tp t Bu,Me LnMe(GaMe 4 ) with primary aniline derivative H 2 NC 6...
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Published in | Chemical science (Cambridge) Vol. 15; no. 1; pp. 3562 - 357 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
England
Royal Society of Chemistry
06.03.2024
The Royal Society of Chemistry |
Subjects | |
Online Access | Get full text |
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Summary: | Terminal rare-earth-metal imide complexes Tp
t
Bu,Me
Ln(NC
6
H
3
iPr
2
-2,6)(dmap) of the mid-late rare-earth elements dysprosium and holmium were synthesized
via
double methane elimination of Lewis acid stabilized dialkyl precursors Tp
t
Bu,Me
LnMe(GaMe
4
) with primary aniline derivative H
2
NC
6
H
3
iPr
2
-2,6 (H
2
NAr
iPr
). Exploiting the weaker Ln-CH
3
[GaMe
3
] interaction compared to the aluminium congener, addition of the aniline derivative leads to the mixed methyl/anilido species Tp
t
Bu,Me
LnMe(HNAr
iPr
) which readily eliminate methane after being exposed to the Lewis base DMAP (&z.dbd;
N
,
N
-dimethyl-4-aminopyridine). Under the same conditions, [AlMe
3
]-stabilized dimethyl rare-earth-metal complexes transform immediately to Lewis acid bridged imides Tp
t
Bu,Me
Ln(μ
2
-NC
6
H
3
Me
2
-2,6)(μ
2
-Me)AlMe
2
(Ln = Dy, Ho). DMAP/THF donor exchange is accomplished by treatment of Tp
t
Bu,Me
Ln(NC
6
H
3
iPr
2
-2,6)(dmap) with 9-BBN in THF while the terminal imides readily insert carbon dioxide to afford carbamate complexes.
Tp
t
Bu,Me
Ln(&z.dbd;NC
6
H
3
iPr
2
-2,6)(dmap) (Ln = Dy, Ho) display the first terminal imides of open-shell mid-sized lanthanides, exhibiting reactivity similar to Chen's seminal scandium terminal imide. |
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Bibliography: | Electronic supplementary information (ESI) available. CCDC For ESI and crystallographic data in CIF or other electronic format see DOI 2312212-2312226 https://doi.org/10.1039/d3sc06584g ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 2041-6520 2041-6539 |
DOI: | 10.1039/d3sc06584g |