6533b7d3fe1ef96bd12614b7
RESEARCH PRODUCT
Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles
James C. FettingerPhilip P. PowerThomas M. BrownFelicitas LipsBrian D. RekkenRolfe H. HerberHeikki M. Tuononensubject
Steric effectsMolecular StructureChemistryLigandStereochemistryGeneral ChemistryBiochemistryLondon dispersion forceCatalysischemistry.chemical_compoundCrystallographyColloid and Surface ChemistryMonomerMolecular geometryOrganometallic CompoundsChalcogensQuantum TheoryMoleculeDispersion (chemistry)MethaneCarbeneta116description
The synthesis and spectroscopic and structural characterization of an extensive series of acyclic, monomeric tetrylene dichalcogenolates of formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch = O, S, or Se; Ar = bulky m-terphenyl ligand, including two new acyclic silylenes) are described. They were found to possess several unusual features-the most notable of which is their strong tendency to display acute interligand, Ch-M-Ch, bond angles that are often well below 90°. Furthermore, and contrary to normal steric expectations, the interligand angles were found to become narrower as the size of the ligand was increased. Experimental and structural data in conjunction with high-level DFT calculations, including corrections for dispersion effects, led to the conclusion that dispersion forces play an important role in stabilizing their acute interligand angles.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2013-06-26 | Journal of the American Chemical Society |