Zur Chemie des Titan(III)-Komplexes [{(Me3Si)2N}2TiCH2SiMe2NSiMe3]–. Insertions-Reaktionen in die Ti–C-Bindung und Redox-Reaktionen
✍ Scribed by Markus A. Putzer; Bernhard Neumüller; Kurt Dehnicke
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- German
- Weight
- 171 KB
- Volume
- 624
- Category
- Article
- ISSN
- 0372-7874
No coin nor oath required. For personal study only.
✦ Synopsis
Professor Achim Mu È ller zum 60. Geburtstag gewidmet Inhaltsu È bersicht.
[Na(12-Krone-4) 2 ][{(Me 3 Si) 2 N} 2 TiCH 2 SiMe 2 NSiMe 3 ] (1) reagiert mit CO und dem Isonitril CNCy (Cy = Cyclohexyl) unter Insertion in die Ti±C-Bindung, wobei nach Umlagerung planare fu È nfgliedrige Titana(III)-Heterocyclen TiOCSiN und TiNCSiN mit exocyclischen C=CH 2 -Gruppen entstehen. Andererseits fu È hrt die Insertion des Isonitrils CNBu t unter neuer Ti(III)±C-Bindungsknu È pfung zu dem prima È ren Insertionsprodukt [Na(12-Krone-4) 2 ][{(Me 3 Si) 2 N} 2 TiC(NBu t )CCH 2 SiMe 2 NSiMe 3 ] (4).
Mit NOBF 4 la È ût sich das Anion von
(3) werden durch Kristallstrukturanalysen charakterisiert.
On the Chemistry of the Titanium(III) Complex [{(Me 3 Si) 2 N} 2 TiCH 2 SiMe 2 NSiMe 3 ] ± . Insertion Reactions into the Ti±C Bond and Redox Reactions Abstract.
[Na(12-crown-4) 2 ][{(Me 3 Si) 2 N} 2 TiCH 2 SiMe 2 NSiMe 3 ] (1) reacts with CO and the isonitrile CNCy (Cy = Cyclohexyl) under insertion into the Ti±C bond. After rearrangement planar five-membered titana(III)-heterocycles TiOCSiN and TiNCSiN with exocyclic C=CH 2 groups are formed. On the other hand, the insertion of CNBu t leads to the primary insertion product 2 ][{(Me 3 Si) 2 N} 2 TiC(NBu t )CCH 2 SiMe 2 NSiMe 3 ] (4) forming a new Ti(III)±C-bond. With NOBF 4 the anion of 1 can be oxydized to form the molecular complex [{(Me 3 Si) 2 N} 2 TiCH 2 SiMe 2 NSiMe 3 ] (5), while with phenylacetylene redox disproportionation occurs, in the course of which the mixed ligand complex [Na(12crown-4) 2 ][{(Me 3 Si) 2 N} 2 Ti(NSiMe 3 )(CH 2 SiMe 2 C≡C±Ph)] (6) can be isolated. 6 and the insertion products [Na(12-crown-4) 2 ]-[{(Me 3 Si) 2 N} 2 TiOC(CH 2 )SiMe 2 NSiMe 3 ] (2) and [Na(12crown-4) 2 ][{(Me 3 Si) 2 N} 2 TiNCyC(CH 2 )SiMe 2 NSiMe 3 ] (3) are characterized by crystal structure determinations.