Geometries, aromatic character, Mulliken charge distribution, and MO diagra
ms of 1,2-aza-, 1,3,2-diaza-, 1,3-aza-, and 1,3,5-diazaphosphinines have be
en calculated and compared to those of phosphinine and pyridine. This study
reveals that the introduction of nitrogen atoms at the position adjacent t
o phosphorus significantly reduces the aromatic delocalization and induces
a [1,4] dipolar character through an increase of the positive charge on the
P atom. This phenomenon does not occur in 1,3-aza- and 1,3,5-diazaphosphin
ines, which exhibit a poor dipolar character. This comparison confirms the
high reactivity of 1,3,2-diazaphosphinines toward alkynes. A [4 + 2] cycloa
ddition reaction between these two types of diazaphosphinines and acetylene
has been modelized. Calculated geometries of the resultant [4 + 2] diazaba
rrelene cycloadducts and that of their respective transition states reveal
that, especially with 1,3,2-diaza isomers, the cycloaddition proceeds via a
disymmetrical pathway that involves the preliminary formation of the P-C b
ond.