Metallacyclodisiladiazanes of Titanium and zirconium; Synthesis, Structure and Polymerization Studies

✍ Scribed by Jäger, Felix ;Roesky, Herbert W. ;Dora, Hendrik ;Shak, Syed ;Noltemeyer, Mathias ;Schmidt, Hans-Geory

• Publisher: Wiley (John Wiley & Sons)
• Year: 1997
• Tongue: English
• Weight: 541 KB
• Volume: 130
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19971300314

✦ Synopsis

A series of metallacyclodisiladiazanes has been prepared. Lithiated (SiMe2NHtBu)z (1) reacts with TiC1, . 2 THF to give (SiMe2NtBu)2TiClz (4). Methylation or fluorination of 4 leads to (SiMe2NtBu)2TiMe, (8) and (SiMezNtBu)zTiFz (9), respectively. The reaction of ZrCL . 2 THF with lithiated 1 or [Si-MezNH(4-FC6H4)I2 (2) yields (SiMezNtBu)zZrClz (5) and [Si-MezN(4-FC6H4)]2ZrC12 . THF (7), respectively. The lithiated ligand [SiMe2NH(2,6-iPr2C6H3)]2 (3) reacts with noncoordinated ZrCll to give [SiMe2N(2,6-iPrzC6H3)]2ZrC12 (6).

X-ray structural analysis of 9 showed it to be a fluorine-bridged dimer in the solid state. Compounds 4,6, 8 and 9 were found to be catalysts for the polymerization of ethylene.