Convenient Synthesis of N-Trimethylsilylaminotitanium Trichlorides

✍ Scribed by Bernd Wrackmeyer; Jürgen Weidinger; Wolfgang Milius

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: German
• Weight: 116 KB
• Volume: 624
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199801)624:1<98::aid-zaac98>3.0.co;2-d

✦ Synopsis

Bis(N-trimethylsilylamino)plumbylenes 1 {[Me 3 Si(R)N] 2 Pb with R = t Bu (a), Me 3 Si (b), 9-(9-borabicyclo[3.3.1]nonyl) (c)} react smoothly with an excess of TiCl 4 to give PbCl 2 and N-trimethylsilylaminotitanium trichlorides 3 a±c. In contrast, the analoguous reaction of the corresponding stannylenes 2 a±c leads to mixtures containing unidentified Ti III compounds, the amides 3 a or 3 b, bis[bis(trimethylsilyl)amino]titanium dichloride 4 b and bis(amino)tin dichlorides 5 a±c. The crystal structure of 3 a was determined by X-ray structural analysis. Compound 3 a is a dimer in the solid state with distorted trigonal pyramidal surroundings of the titanium atoms. Each titanium atom bears two l 2 -Cl ligands which are in axial (d Ti±Cl = 250.7(1) pm) and equatorial positions (d Ti±Cl = 247.0(1) pm) and two terminal chloro ligands, one in axial (d Ti±Cl = 228.0(1) pm) and one in equatorial position (d Ti±Cl = 221.1(1) pm). The equatorial Ti±N bonds are short (183.8(2) pm).