188599-46-4Relevant academic research and scientific papers
Expanding the steric coverage offered by bis(amidosilyl) chelates: Isolation of low-coordinate N-heterocyclic germylene complexes
Liew, Sean K.,Al-Rafia, S. M. Ibrahim,Goettel, James T.,Lummis, Paul A.,McDonald, Sean M.,Miedema, Leah J.,Ferguson, Michael J.,McDonald, Robert,Rivard, Eric
experimental part, p. 5471 - 5480 (2012/07/01)
The synthesis and coordination chemistry of a series of dianionic bis(amido)silyl and bis(amido)disilyl, [NSiN] and [NSiSiN], chelates with N-bound aryl or sterically modified triarylsilyl (SiAr3) groups is reported. In order to provide a consistent comparison of the steric coverage afforded by each ligand construct, various two-coordinate N-heterocyclic germylene complexes featuring each ligand set were prepared and oxidative S-atom transfer chemistry was explored. In the cases where clean oxidation transpired, sulfido-bridged centrosymmetric germanium(IV) dimers of the general form [LGe(μ-S)]2 (L = bis(amidosilyl) ligands) were obtained in lieu of the target monomeric germanethiones with discrete Ge=S double bonds. These results indicate that the reported chelates possess sufficient conformational flexibility to allow for the dimerization of LGe=S units to occur. Notably, the new triarylsilyl groups (4-RC6H4)3Si- (R = tBu and iPr) still offer considerably expanded degrees of steric coverage relative to the parent congener, -SiPh3, and thus the use of substituted triarylsilyl groups within ligand design strategies should be a generally useful concept in advancing low-coordination main group and transition-metal chemistry.
Metallacyclodisiladiazanes of titanium and zirconium; synthesis, structure and polymerization studies
Jaeger, Felix,Roesky, Herbert W.,Dorn, Hendrik,Shah, Syed,Noltemeyer, Mathias,Schmidt, Hans-Georg
, p. 399 - 403 (2007/10/03)
A series of metallacyclodisiladiazanes has been prepared. Lithiated (SiMe2NH(Bu)2 (1) reacts with TiCl4 2 THF to give (SiMe2N/Bu)2TiCl2 (4). Methylation or fluorination of 4 leads to (SiMe2NfBu)2TiMe2 (8) and (SiMe2N(Bu)2TiF2 (9), respectively. The reaction of ZrCl4 2 THF with lithiated 1 or [SiMe2NH(4-FC6H4)]2 (2) yields (SiMe2NfBu)2ZrCl2 (5) and [Si-Me2N(4-FC6H4)]2ZrCl2 ·THF (7), respectively. The lithiated ligand [SiMe2NH(2,6-iPr2C6H3)]2 (3) reacts with noncoordinated ZrCl4 to give [SiMe2N(2,6-/Pr2C6H3)]2ZrCl2 (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. VCH Vcrlagsgcsellschaft mbH,.
