10.1021/ic101485a.s002
S. M. Ibrahim Al-Rafia
S.
M. Ibrahim Al-Rafia
Paul A. Lummis
Paul A.
Lummis
Michael J. Ferguson
Michael J.
Ferguson
Robert McDonald
Robert
McDonald
Eric Rivard
Eric
Rivard
Low-Coordinate Germylene and Stannylene Heterocycles featuring Sterically Tunable Bis(amido)silyl Ligands
American Chemical Society
2010
iPr
2C
2Si
group 14 centers
chalcogen sources
sulfido complexes
steric protection
dimeric oxo
SiPh
Structural analyses
S 8
3NO
Stannylene Heterocycles
metallylene
steric bulk
Dipp group
NSiN chelate
2010-10-18 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Low_Coordinate_Germylene_and_Stannylene_Heterocycles_featuring_Sterically_Tunable_Bis_amido_silyl_Ligands/2721085
A series of monomeric heterocyclic metallylenes [{<sup><i>i</i></sup>Pr<sub>2</sub>Si(NR)<sub>2</sub>}M:] (M = Ge and Sn; R = Dipp = 2,6-<i><sup>i</sup></i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub> or SiPh<sub>3</sub>) have been prepared. Preliminary atom-transfer chemistry involving the new low-valent germylenes with the chalcogen sources Me<sub>3</sub>NO and S<sub>8</sub> yielded the corresponding dimeric oxo- and sulfido complexes (e.g., [{<i><sup>i</sup></i>Pr<sub>2</sub>Si(NDipp)<sub>2</sub>}Ge(μ-E)]<sub>2</sub>; E = O and S). Structural analyses of the metallylenes and their oxidized products reveal that incorporation of the umbrella-shaped triarylsilyl groups (SiPh<sub>3</sub>) within the NSiN chelate confers additional steric protection about the group 14 centers relative to a Dipp group. The inclusion of sterically modifiable −SiAr<sub>3</sub> (Ar = aryl) units as part of a bis(amido) ligand array represents a new approach in this field and holds considerable promise with regard to attaining increasingly higher degrees of steric bulk.