Silver Complexes of Cyclic Hexachlorotriphosphazene

Abstract

The first solid-state structures of complexed P3N3X6 (X = halogen) are reported for X = Cl. The compounds were obtained from P3N3Cl6 and Ag[Al(OR)4] salts in CH2Cl2/CS2 solution. The very weakly coordinating anion with R = C(CF3)3 led to the salt Ag(P3N3Cl6)2+[Al(OR)4]- (1), but the more strongly coordinating anion with R' = C(CH3)(CF3)2 gave the molecular adduct (P3N3Cl6)AgAl(OR')4 (3). Crystals of [Ag(CH2Cl2)(P3N3Cl6)2]+[Al(OR)4]- (2), in which Ag+ is coordinated by two phosphazene and one CH2Cl2 ligands, were isolated from CH2Cl2 solution. The three compounds were characterized by their X-ray structures, and 1 and 3 also by NMR and vibrational spectroscopy. Solution and solid-state 31P NMR investigations in combination with quantum chemically calculated chemical shifts show that the 31P NMR shifts of free and silver-coordinated P3N3Cl6 differ by less than 3 ppm and indicate a very weakly bound P3N3Cl6 ligand in 1. The experimental silver ion affinity (SIA) of the phosphazene ligand was derived from the solid-state structure of 3. The SIA shows that (PNCl2)3 is only a slightly stronger Lewis base than P4 and CH2Cl2, while other ligands such as S8, P4S3, toluene, and 1,2-Cl2C2H4 are far stronger ligands towards the silver cation. The energetics of the complexes were assessed with inclusion of entropic, thermal, and solvation contributions (MP2/TZVPP, COSMO). The formation of the cations in 1, 2, and 3 was calculated to be exergonic by delta(r)G(degrees)(CH2Cl2) = -97, -107, and -27 kJ mol(-1), respectively. All prepared complexes are thermally stable; formation of P3N3Cl5+ and AgCl was not observed, even at 60 degrees C in an ultrasonic bath. Therefore, the formation of P3N3Cl5+ was investigated by quantum chemical calculations. Other possible reaction pathways that could lead to the successful preparation of P3N3X5+ salts were defined.

Tetraalkylammonium Salts of Weakly Coordinating Aluminates: Ionic Liquids, Materials for Electrochemical Applications and Useful Compounds for Anion Investigation

“…Especially the P À X cations are incompatible with all other anion types. This also holds for a series of silver and copper(I) complexes with very weakly basic ligands, for example, P 4 , [29,30] P 4 S 3 , [31,32] S 8 , [33] P 3 N 3 Cl 6 , [34] or C 2 H 4 . [35,36] Since the starting materials to prepare compounds of the fluorinated aluminates are commercially available (best at P&M Invest Russia; http:// www.fluorine.ru) and the synthesis of the lithium aluminate salts [37][38][39] is a simple high yield procedure that we have performed in scales up to 250 g per batch, [40] it only appeared logical to extend the available substance classes to [NR 4 ] + salts.…”

Dynamics and Counterion‐Dependence of the Structures of Weakly Bound Ag+–P4S3 Complexes

“…+ , [5,6] [Ag(S 8 ) 2 ] + , [1] [Au(Xe) 4 ] + , [14] [AgA C H T U N G T R E N N U N G (P 3 N 3 Cl 6 ) n ] + , [3] [AgA C H T U N G T R E N N U N G (C 2 H 2 ) n ] + , [15] {[AgA C H T U N G T R E N N U N G {Cp*Fe(P 5 )} 2 ] + ) 1 , [4] or [AgA C H T U N G T R E N N U N G (C 2 H 4 ) n ]…”

“…Only isolated dimeric dications are formed with the largest cation, but polymeric species are obtained with all other smaller aluminates. Thermodynamic Born-Haber cycles, DFT calculations, as well as solution NMR and ESI mass spectrometry indicate that 8 exhibits an equilibrium between the dication [Ag 2 A C H T U N G T R E N N U N G (P 4 S 3 ) 6 ] 2 + (in the solid state) and two [AgA C H T U N G T R E N N U N G (P 4 S 3 ) 3 ]…”

“…[1][2][3][4][5][6] The first P 4 S 3 complex, [Mo(CO) 5 A C H T U N G T R E N N U N G (P 4 S 3 )], was reported by Cordes and co-workers in 1974. [7] In this compound, as well as in the rare later examples, such as [(np 3 )NiA C H T U N G T R E N N U N G (P 4 S 3 )] [1,2] (np 3 : tris(2-(diphenylphosphino)ethyl)amine) or (P 4 S 3 )A C H T U N G T R E N N U N G (BX 3 ) (X: Br, I), [8] the P 4 S 3 cage is bound through the apical P atom.…”

Synthesis and Structural Characterization of Singly, Doubly, and Triply Bridged Derivatives of Hexachlorocyclotriphosphazene with Bis(2-hydroxyethyl) Ether and 2,2-dimethylpropane-1,3-diol

“…SILAH AND S. TURE 15.2 (P(OR)Cl), 2 J PP = 67.2 Hz. 13 C NMR (CDCl 3 ): δ = 75.6 (d, 2 J PC = 6.9 Hz, POC), 31.5 (d, 3 J PC = 5.8 Hz, POCC), 22.4 (s, CH 3 ), 21.9 (s, CH 3 ).…”