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Reactions of Heteroallenes with Salan-based Ti(IV) Complexes: A Joint Experimental and Computational Study.
- Source :
-
Chemistry, an Asian journal [Chem Asian J] 2024 May 17; Vol. 19 (10), pp. e202400165. Date of Electronic Publication: 2024 Mar 11. - Publication Year :
- 2024
-
Abstract
- The reaction of Ti(NMe <subscript>2</subscript> ) <subscript>4</subscript> with the salan ligand precursor H <subscript>2</subscript> N <subscript>2</subscript> O <subscript>2</subscript> H <subscript>2</subscript> led to the formation of [(L*)Ti(NHMe <subscript>2</subscript> ) <subscript>2</subscript> ] (L*=N <subscript>2</subscript> O <subscript>2</subscript> <superscript>4-</superscript> ) that forms [(H <subscript>2</subscript> N <subscript>2</subscript> O <subscript>2</subscript> )TiCl <subscript>2</subscript> ] upon reaction with two equiv. of Me <subscript>3</subscript> SiCl. [(L*)Ti(py) <subscript>2</subscript> ] was obtained from the reaction of [Ti(N <superscript>t</superscript> Bu)Cl <subscript>2</subscript> (py) <subscript>3</subscript> ] with the sodium salt H <subscript>2</subscript> N <subscript>2</subscript> O <subscript>2</subscript> Na <subscript>2</subscript> . Treatment of [(L*)Ti(NHMe <subscript>2</subscript> ) <subscript>2</subscript> ] with two equiv. of <superscript>t</superscript> BuNCO led to the insertion of the isocyanate molecules into the Ti-N <subscript>salan</subscript> bonds with the formation of [{L*(N( <superscript>t</superscript> Bu)CO) <subscript>2</subscript> }Ti]. Conversely, the reaction of [(H <subscript>2</subscript> N <subscript>2</subscript> O <subscript>2</subscript> )Ti(O <superscript>i</superscript> Pr) <subscript>2</subscript> ] with two equiv. of <superscript>t</superscript> BuNCO led to the insertion of one isocyanate molecule into a Ti-N <subscript>salan</subscript> bond with the formation of [{(HN <subscript>2</subscript> O <subscript>2</subscript> )(N( <superscript>t</superscript> Bu)CO)}Ti(O <superscript>i</superscript> Pr)]. Computational studies were performed to gain insight into the reactivity of isocyanates with salan-based Ti(IV) complexes.<br /> (© 2024 Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1861-471X
- Volume :
- 19
- Issue :
- 10
- Database :
- MEDLINE
- Journal :
- Chemistry, an Asian journal
- Publication Type :
- Academic Journal
- Accession number :
- 38403858
- Full Text :
- https://doi.org/10.1002/asia.202400165