Synthese, Eigenschaften und Kristallstrukturen der Titan(III)‐Amido‐Komplexe Ti[N(SiMe 3 ) 2 ] 3 , [TiCl 2 {N(SiMe 3 ) 2 }(THF) 2 ] und [Na(12‐Krone‐4) 2 ][TiCl 2 {N(SiMe 3 ) 2 } 2 ]

Syntheses, Properties, and Crystal Structures of the Titanium(III) Amido Complexes Ti[N(SiMe 3 ) 2 ] 3 , [TiCl 2 {N(SiMe 3 ) 2 }(THF) 2 ], and [Na(12‐Crown‐4) 2 ][TiCl 2 {N(SiMe 3 ) 2 } 2 ] TiCl 3 (THF) 3 reacts with NaN(SiMe 3 ) 2 to furnish [TiCl 2 {N(SiMe 3 ) 2 }(THF) 2 ] ( 1 ), whereas in the presence of 12‐crown‐4 the ionic amido complex [Na(12‐crown‐4) 2 ][TiCl 2 {N(SiMe 3 ) 2 } 2 ] ( 5 ) is obtained besides [Na(12‐crown‐4) 2 ][TiCl 4 (THF)] ( 4 ). On the other hand, the titanium(III) amido complex Ti[N(SiMe 3 ) 2 ] 3 ( 2 ), the crystal structure of which was solved, reacts with NaN(SiMe 3 ) 2 in the presence of 12‐crown‐4 with deprotonation of one of the methyl groups to give the carbometalated complex [Na(12‐crown‐4) 2 ][Ti{N(SiMe 3 ) 2 } 2 {N(SiMe 3 CH 2 )}] ( 3 ).