The N-donor stabilised cyclotriphosphazene hexacation [P3N3(DMAP)6]6+

Abstract

The cyclotriphosphazene P(3)N(3)Cl(6) reacts with six equivalents of DMAP (4-(dimethylamino)pyridine) in superheated chloroform to form crystals of composition [P(3)N(3)(DMAP)(6)]Cl(6).19CHCl(3) comprising [P(3)N(3)(DMAP)(6)](6+) ions, which host five chloride ions in basket-type cavities on either side of the ring and at equatorial positions via tetradentate ortho-H-donor arrangements.

Coordination Complexes of Ph3Sb2+ and Ph3Bi2+: Beyond Pnictonium Cations

“…Indeed, a number of cationic complexes containing tetrahedral P V acceptor centers have been structurally characterized, [7][8][9][10][11] although in all but a single case [7] ligand coordination is facilitated by a low coordination number at a phosphorus center involved in multiple bonding.Here we report the synthesis and comprehensive characterization of complexes with the generic formula [Ph 3 PnL 2 ] 2+ for Pn = Sb or Bi, and L = OPPh 3 or 4-(dimethylamino)pyridine (dmap), which demonstrate a preference for axial coordination of the L donors. In addition, we report analogous complexes of Ph 3 Pn 2+ for Pn = Sb or Bi, with the chelating donor 2,2'-bipyridine (bipy).…”

Why Do Five Ga+ Cations Form a Ligand‐Stabilized [Ga5]5+ Pentagon and How Does a 5:1 Salt Pack in the Solid State?

“…To our knowledge,a ni onic AX 5 lattice constructed from an isolated pentacation A 5+ and five univalent counterions X À is hitherto unknown. Formally,such structures may exist, but as exemplarily shown for the compound [P 3 N 3 (dmap) 6 ]Cl 6 [25] that contains af ormal hexacation [P 3 N 3 (dmap) 6 ] 6+ ,s uch formally highly charged system do accommodate many of the counterions in ahost-guest assembly;inthis example,five out of six chloride ions.S oe ssentially,t he ion packing in the [P 3 N 3 (dmap) 6 ]Cl 6 salt is that of a1:1 salt as in [P 3 N 3 (dmap) 6 -(Cl 5 )]Cl. By contrast, 1 forms atruly ionic lattice.All ions in 1 are arranged in ahexagonal primitive lattice that is slightly distorted due to the larger size of the pentacation (Figure 2).…”

Interpniktogenkationen: Neue Perspektiven in der Koordinationschemie

“…[35] Eine Reihe von Amin-und Pyridin-stabilisierten (L) Phosphor-zentrierten Kationen kann durch die Verdrängung des Triflatanions in Mes*NPOTf erhalten werden, was durch Derivate von [L-PNMes*][OTf] (Abbildung 4) als Komplexe mit einzähnigen, zweizähnigen, dreizähnigen und verbrückenden Liganden veranschaulicht wird. [78] 6 gefunden, wobei viele Bindungen länger sind als die Summe der Kovalenzradien der zwei Elemente (S CR = 1.80 ). [78] 6 gefunden, wobei viele Bindungen länger sind als die Summe der Kovalenzradien der zwei Elemente (S CR = 1.80 ).…”

“…In dem Hexakation sind zwei dmap-Liganden zu jedem Phosphorzentrum gebunden (Abbildung 6 b) und die Chloridanionen befinden sich an drei verschiedenen Stellen. b) Struktur desHexakations im Festkçrper [78]. Obgleich die Phosphorzentren gleichwertig sind, kann der Komplex in einer Art betrachtet werden, dass er eine ungewçhnliche Wechselwirkung von Tripyrazol mit P 3+ -Akzeptor (Klasse 2C) widerspiegelt.…”