First principles study of the evolution of the properties of neutral and charged phosphorus clusters

Quantitative analysis of bonding in P4 clusters

“…There is also some evidence of the formation of the tetraphosphorus anion [14]. Other data [15] attest that the P 4 fragment has cage, plane, zigzag, and other intermediate configurations.…”

“…Calculations of P n clusters (n = 2-89) have been carried out and the geometry and relative stability of the isomers evaluated [15,[17][18][19]. However, the detailed picture of the chemical bond in the phosphorus clusters has not been examined until now.…”

“…It was also assumed that the presence of π -bonds influences the structure of a P 4 molecule [18]. At the same time, the assumption about the possible linear structure of the polymer consisting of open P 4 fragments [20] was not confirmed [15].…”

Access to Phosphorus‐Rich Zirconium Complexes

“…[19] The cuneane structure is also calculated to be the minimum structure of a hypothetical P 8 molecule. [20] In 3, the cuneane core is made up by six phosphorus atoms and two carbon atoms with the ZrCp'' 2 fragment inserted into one P À P bond of the cuneane core; this core has bond lengths in the usual range of PÀP, CÀP, and CÀC single bonds. The PÀP bond lengths vary between 2.181(2) and 2.225(3) and are in the same range as the P À P bonds in the P 8 core of (1,2-C 6 H 4 ) 2 P 8 [19d] or in the tricyclic compound [(1,2-C 6 H 4 ) 2 H 2 P 6 {W(CO) 5 } 4 ].…”

Der Zugang zu Phosphor‐reichen Zirconiumkomplexen

“…[19] Die Cuneanstruktur wurde als Minimumstruktur des hypothetischen P 8 -Moleküls berechnet. [20] In 3 wird das Cuneangerüst durch sechs Phosphoratome und zwei Kohlenstoffatome gebildet, mit einem ZrCp'' 2 -Fragment, das in eine P-P-Bindung des Cuneangerüsts eingebaut ist. Es zeigt Bindungslängen im üblichen Bereich von P-P-, C-P-und C-CEinfachbindungen.…”