Branched alkanes have contrasting stabilities.
Bond separation reactions of highly branched alkanes are used to assess (de)stabilizing interactions associated with various 1,3-nonbonded substituent patterns. While n- and singly methylated alkanes show positive bond separation energies (BSEs), which increase systematically along the series, permethylated alkanes are characterized by decreasing BSEs. Analysis shows that singly methylated alkanes are more stabilized than linear alkane chains and that the unique destabilizing feature of permethylated alkanes arises from the close proximity of bulky methyl groups causing highly distorted geometries along the carbon backbone.
Gonthier
Jérôme F
JF
Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.
Wodrich
Matthew D
MD
Steinmann
Stephan N
SN
Corminboeuf
Clémence
C