Synthesis, Structure, Strain Energy, and Excess Strain of a
Phospha[3]triangulane
Koop Lammertsma
Bing Wang
Jui-Te Hung
Andreas W. Ehlers
Gary M. Gray
10.1021/ja9905896.s001
https://acs.figshare.com/articles/journal_contribution/Synthesis_Structure_Strain_Energy_and_Excess_Strain_of_a_Phospha_3_triangulane/3674568
(7-Phenyl-7-phosphadispiro[2.0.2.1]heptane)pentacarbonyltungsten (<b>8</b>), a phospha[3]triangulane, was
synthesized from bicyclopropylidene. Its single-crystal X-ray structure determination is reported. Comparison
of the crystal structure data with those of the related phosphaspiropentane <b>7</b> and phosphirane <b>6</b> complexes
suggests that the phosphirane ring tightens when the number of spiro atoms is increased. This is supported by
the B3LYP and MP2/6-31G* computed geometries of the uncomplexed parent systems. Ab initio calculated
heats of formation and strain energies (SE) are reported for the parent phosphirane <b>11</b>, phosphaspiropentane
<b>12</b>, and phospha[3]triangulane <b>13</b> using both G2MP2 theory and ring separation reactions. Our best estimates
for the Δ<i>H</i><sub>f</sub> of <b>11</b>, <b>12</b>, and <b>13</b> are 18.3, 48.4, and 78.2 kcal/mol, respectively, with corresponding SE values
of 21.3, 54.7, and 87.9 kcal/mol. For comparison, the slightly modified G2MP2 method was also applied to
cyclopropane <b>1</b>, spiropentane <b>2</b>, and [3]triangulane <b>3</b> to give respective Δ<i>H</i><sub>f</sub> values of 12.6, 44.3, and 75.3
kcal/mol, with corresponding SEs of 28.0, 64.6, and 100.5 kcal/mol, all of which are in excellent agreement
with reported experimental data. These strain energies suggest that the excess strain per spiro atom is 5.3
kcal/mol for phospha[<i>n</i>]triangulanes, which is smaller than the 8.6 kcal/mol determined from the heat of
combustion measurements for the [<i>n</i>]triangulanes.
1999-12-02 00:00:00
strain energies
phosphirane 6 complexes
triangulane
G 2MP method
Δ H f
crystal structure data
phospha
kcal
3LYP
Δ H f values
SE
ring separation reactions
parent phosphirane 11
G 2MP theory
uncomplexed parent systems