Expanding the steric coverage offered by bis(amidosilyl) chelates: isolation of low-coordinate N-heterocyclic germylene complexes.
Inorg Chem
; 51(9): 5471-80, 2012 May 07.
Article
em En
| MEDLINE
| ID: mdl-22530833
ABSTRACT
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 (SiAr(3)) 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 GeâS double bonds. These results indicate that the reported chelates possess sufficient conformational flexibility to allow for the dimerization of LGeâS units to occur. Notably, the new triarylsilyl groups (4-RC(6)H(4))(3)Si- (R = (t)Bu and (i)Pr) still offer considerably expanded degrees of steric coverage relative to the parent congener, -SiPh(3,) 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.
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MEDLINE
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En
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Inorg Chem
Ano de publicação:
2012
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Article