Mono, bis, and tris(phosphoramidate) titanium complexes: synthesis, structure, and reactivity investigations
A series of variously substituted phosphoramidate titanium complexes bearing dimethylamido ligands are reported. Aryl-substituted ligands impart crystallinity to the systems and allow for the elucidation of the molecular structures via X-ray crystallography. Higher-substituted complexes, including a...
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2019-07, Vol.48 (26), p.9782-979 |
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Hauptverfasser: | , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | A series of variously substituted phosphoramidate titanium complexes bearing dimethylamido ligands are reported. Aryl-substituted ligands impart crystallinity to the systems and allow for the elucidation of the molecular structures
via
X-ray crystallography. Higher-substituted complexes, including a tris(phosphoramidate)mono(dimethylamido) complex, were isolated and characterized in the solid state, as well as in solution using variable temperature
1
H and
31
P NMR spectroscopy. The steric bulk possessed by this ligand system, relative to amidate and ureate ligands, has allowed access to a mono(phosphoramidate)tris(dimethylamido) complex. The first solid-state-molecular structure of a mono-ligated 1,3-
N
,
O
chelated complex of titanium is reported and compared to the respective bis- and tris-analogues. These complexes were screened for hydroaminoalkylation activity between secondary amines and terminal alkenes and the intramolecular hydroamination of a terminal aminoalkene. Mono(phosphoramidate)tris(dimethylamido) complexes were screened
in situ
and found to be more active than their respective bis(
N
,
O
)-chelated analogues. The elucidation of these complexes allows for a direct comparison to other
N
,
O
-chelates of early transition metals, particularly in their hydroaminoalkylation and hydroamination reactivity.
A series of variously substituted phosphoramidate titanium complexes bearing dimethylamido ligands are reported. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c9dt00911f |