Diana N. Zeiger

The strain energy of fluorinated cyclopropanes: quantum chemical realization of homodesmotic, diagonal and ultradiagonal approaches

Abstract The complete series of fluorinated cyclopropanes (0–6 fluorines) were studied by ab initio (Hartree–Fock) quantum chemical calculations with the 6-311G ∗∗ basis set with explicit zero-point energies and thermal corrections. From these calculated total energies (enthalpies) and those of appropriate reference species, the strain energies of these cyclopropanes were calculated using the homodesmotic, diagonal and ultradiagonal approaches. Our results are consistent with the earlier experience (both experimental and computational) that hexafluorocyclopropane is considerably more strained than the parent hydrocarbon: other comparisons between molecules and between methods is thwarted by lack of experimental data.

Interplay of thermochemistry and Structural Chemistry, the journal (volume 22, 2011, issues 4–6) and the discipline

In the current review of the journal Structural Chemistry, the content of the issues 4–6 for the calendar year 2011 is related to thermochemistry. To the summary of each paper, a brief thermochemical commentary is added.

Interplay of thermochemistry and structural chemistry, the journal (volume 24, 2013, issues 5–6) and the discipline

Abstract The contents of issues 5 and 6 for the calendar year 2013 are summarized in the current review of the journal Structural Chemistry. A brief thermochemical commentary is added to the summary of each paper.

Interplay of thermochemistry and structural chemistry, the journal (volume 25, 2014, issues 1–2) and the discipline

The contents of issues 1 and 2 for the calendar year 2014 are summarized in the current review of the journal Structural Chemistry. A brief thermochemical commentary is added to the summary of each paper.

Interplay of thermochemistry and Structural Chemistry, the journal (volume 23, 2012, issues 4–6) and the discipline

In the current review of the journal Structural Chemistry, the contents of the issues 4–6 for the calendar year 2012 are related to thermochemistry. A brief thermochemical commentary is added to the summary of each paper.

Interplay of thermochemistry and Structural Chemistry, the journal (volume 23, 2012, issues 1–3) and the discipline

In the current review of the journal Structural Chemistry, the contents of the issues 1–3 for the calendar year 2012 are related to thermochemistry. A brief thermochemical commentary is added to the summary of each article.

Interplay of thermochemistry and Structural Chemistry, the journal (Volume 25, 2014, Issues 3–4) and the discipline

The contents of issues 3 and 4 for the calendar year 2014 are summarized in the current review of the journal Structural Chemistry. A brief thermochemical commentary is added to the summary of each paper.

Interplay of thermochemistry and Structural Chemistry, the journal (Volume 25, 2014, Issues 5–6) and the discipline

The contents of issues 5 and 6 for the calendar year 2014 are summarized in the current review of the journal Structural Chemistry. A brief thermochemical commentary is added to the summary of each paper.

Strainless reference states for poly- and perfluorocycloalkanes: the ultradiagonal strain energy approach

Abstract It is well-established that the strain energy of cycloalkanes is affected by fluorination. While the strain energies of cyclopropane and cyclobutane are very nearly equal, perfluorination markedly increases the strain energy of the former and correspondingly decreases the latter. The numerical value for the strain energy of a given molecule is model-dependent. We discuss the strain energies of fluorinated cycloalkanes in terms of the “ultradiagonal” approach, a method earlier found useful for the understanding of fluorinated cyclopropanes and other species containing three-membered rings.

Interplay of thermochemistry and Structural Chemistry, the journal (Volume 27, 2016, Issues 5 and 6) and the discipline

The contents of issues 5 and 6 of Structural Chemistry from the calendar year 2016 are summarized in the present review. A brief thermochemical commentary and possible guidelines for future research have been added to the summary of each paper.