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aryloxide-amidinate group 4 metal complexes
A N -aryloxide-amidine ligand (H 3 L), integrating phenoxide (PhO − ) and amidine ligands through methylene linkers, has been synthesized from 2-(aminomethyl)-6-( tert -butyl)phenol in two steps. Upon reacting the deprotonated H 3 L ligand with group 4 metal chloride M IV Cl 4 , a corresponding (LM...
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| Published in: | Dalton transactions : an international journal of inorganic chemistry 2023-08, Vol.52 (33), p.11565-11570 |
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| Main Authors: | , , , |
| Format: | Article |
| Language: | |
| Online Access: | Get full text |
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| Summary: | A
N
-aryloxide-amidine ligand (H
3
L), integrating phenoxide (PhO
−
) and amidine ligands through methylene linkers, has been synthesized from 2-(aminomethyl)-6-(
tert
-butyl)phenol in two steps. Upon reacting the deprotonated H
3
L ligand with group 4 metal chloride M
IV
Cl
4
, a corresponding (LM
IV
-Cl)
2
dimer could be obtained. The coordination modes exhibit variation depending on the radius of the metal ions. In the case of (LTi
IV
-Cl)
2
, the two ArO
−
arms from the same ligand bond to two different Ti(
iv
) centers, while in the case of (LZr
IV
/Hf
IV
-Cl)
2
, both ArO
−
arms coordinate with the same metal center. Moreover, the two C-N bonds in the amidinate moiety are localized in (LTi
IV
-Cl)
2
, whereas they delocalize in (LZr
IV
-Cl)
2
. Notably, (LHf
IV
-Cl)
2
could further react with one equivalent of HfCl
4
, yielding the binuclear metal azide in the presence of KN
3
and LiCl, where the coordination mode of the amidinate moiety changed from the bidentate chelating type to the bimetallic bridging coordination.
A
N
-aryloxide-amidine ligand was prepared in two steps. And the corresponding Ti, Zr, and Hf complexes were obtained. |
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| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d3dt01767b |