The synthesis of 2,4,6-triphenylphosphinine has been revisited and a general protocol for the preparation of such low-coordinate phosphorus compounds in good to excellent yields could be established. This allows to investigate several aspects of the chemistry of 2,4,6-triarylphosphinine, such as the reaction with in situ generated benzyne to give 2,4,6-triphenylphosphabarrelene. The corresponding 2,4,6-triphenylphosphabarrelene-selenide could be characterized crystallographically for the first time and the structural and electronic properties of this cage-compound in comparison to classical triarylphosphines could be evaluated. Moreover, [(L)W(CO)5)] complexes of both 2,4,6-triphenylphosphinine and 2,4,6-triphenylphosphabarrelene were prepared and characterized by means of X-ray crystallography. This allowed for the first time a direct structural comparison of these related phosphorus compounds, coordinated to the same metal fragment.