Small Neutral Pn Molecules

Abstract

Neutral P6 can be generated in the gas phase from CpP6 and detected by mass spectrometry. Small, neutral Pn molecules, apart from white phosphorus (tetrahedral P4) are scarce. The picture shows the P6 isomers that are isoelectronic to the five (CH)6 valence isomers. The calculated stability decreases from left to right; thus a benzvalene structure (far left) is assumed for the P6 molecule detected in the gas phase. Futhermore, the predictions from theory as well as the complex chemical stabilization of small Pn molecules are presented.

Activation of White Phosphorus by Reduction in the Presence of a Zirconium Diamidodiphosphine Macrocycle: Formation of a Bridging Square‐Planar cyclo‐P4 Unit

“…Planar P 4 units that are formally dianionic are known; for example, the compound Cs 2 P 4 ·2 NH 3 for which the X-ray crystal structure shows [12] a planar square of phosphorus atoms with P À P bond lengths that are 2.146(1) , significantly shorter than those observed in 3. Other P 4 units exist bound to transition-metal complexes in a variety of ways, [13][14][15][16][17][18][19][20] but none match what is reported in this investigation. Mononuclear Group 5 complexes of P 4 are known, for example, [Cp*Nb(CO) 2 (h 4 -P 4 )] (Cp* = C 5 Me 5 ; Scheme 1) and its tantalum congener [21,22] have been isolated; in addition, the Group 9 complex [RhCl(PPh 3 ) 2 (h 2 -P 4 )] is known wherein the P 4 unit is essentially an intact tetrahedral array of phosphorus atoms (Scheme 1).…”

“…[24] Other dinuclear and polynuclear systems have been reported with bridging P 4 units many of which formally involve a neutral or a dianionic P 4 moiety. [1,13,17,18,25] The reactivity of the dizirconium P 4 complex 3 has not yet been extensively examined. However, addition of two equivalents of KC 8 to a toluene solution of 3 results in the incorporation of two potassium ions; this new complex 4 can be isolated a dark purple solid and analyzes for [{(P 2 N 2 )Zr} 2 P 4 K 2 ].…”

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

“…Gruppe sind weiter verbreitet als die der Tetrelelemente. Neutrale P 4 ‐ und As 4 ‐Moleküle als Liganden sind in der Literatur ausführlich zusammengefasst worden186, 234 und werden daher hier nicht im Detail diskutiert. In Gegenwart schwach koordinierender Gegenionen wurde kürzlich über die Koordination zweier tetraedrischer P 4 ‐Moleküle an Cu I unter Bildung von [Cu(P 4 ) 2 ] + berichtet.…”

Carbon-free D3d [E3ME3]2− (E=P, As; M=Ni, Pd, Pt): The smallest inorganic sandwich complexes with aromatic η3-P 3 − and η3-As 3 − ligands

“…Being in a diagonal relationship with C in the periodic table, P is electronically equivalent (isolobal) to a CH group and can form various complexes with substituent-free cyclic and acyclic phosphorus ligands [1][2][3][4][5][6][7][8][9][10][11][12][13]. Other group 15 elements, especially the immediate follower As, possess certain similarities to P. The successful coordinative stabilization of cyclo-E 3 7] with a cyclo-P n (n = 3-6) middle deck.…”

“…Other group 15 elements, especially the immediate follower As, possess certain similarities to P. The successful coordinative stabilization of cyclo-E 3 7] with a cyclo-P n (n = 3-6) middle deck. The first totally carbon-free inorganic metallocene [Ti(P 5 ) 2 ] 2 containing two aromatic  5 -P 5  ligands was successfully synthesized and characterized in 2002, in which cyclo-P 5  serves as an acceptor [14].…”