Phosphazene. XII. Bis‐ und Tris‐ (trichlorphosphazo)‐methyl‐hexachloroantimonate

Schmidpeter, Alfred; Düll, Krista; Böhm, R.

doi:10.1002/zaac.19683620110

Cited by 7 publications

(3 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…torsion angles as predicted for this compound [13]. The comparison of the four independent cations in the two compounds shows the agreement in the conformation (see Fig.…”

mentioning

confidence: 58%

“…Both the cations show cis-trans conformations with respect to their Cl-C-N-P torsion angles instead of the most symmetric (C2 v -mm2) cis-cis conformation. A trans-trans conformation is not possible by sterical hindrance of the two NPCI3 groups.The related compound bis(trichlorophosphazeno)methyl-carbenium hexachloroantimonate, [CH3-C(NPCl3)2]SbCl<s, can be synthesized by reaction of ethanamidine with PCI5[13]. Once again there are two formula units in the asymmetric unit of the triclinic cell, and both the cations show cis-trans conformations with respect to their CMC-C-N-P…”

mentioning

confidence: 99%

See 1 more Smart Citation

Structural Chemistry of Non - Cyclic Phosphazenes

Belaj¹

1996

Phosphorus, Sulfur, & Silicon & the Related Elements

View full text Add to dashboard Cite

The crystal structures of some open-chained trichlorophosphazenes, the , NPCb groups attached to carbon, were determined at low temperature (90K, 100K), and the structures were compared in order to show the conformational variability of these compounds. This investigation comprises the structures of the : cations in [C1-C(NPC1 3 ) 2 ]PCU and in [CH 3 -C(NPCl3)2]SbCl 6) and the molecular structures of 2,2,4-trichloro-6-trichlorophosphazeno-l,3,5,2X 5 -triazaphosphorine, C2CI6N4P2, and of a triclinic and a monoclinic modification.of 2,4,6-tris(trichloro-' phosphazeno)-l,3,5-triazine, C3CI9N6P3.

show abstract

“…torsion angles as predicted for this compound [13]. The comparison of the four independent cations in the two compounds shows the agreement in the conformation (see Fig.…”

mentioning

confidence: 58%

mentioning

confidence: 99%

Structural Chemistry of Non - Cyclic Phosphazenes

Belaj¹

1996

Phosphorus, Sulfur, & Silicon & the Related Elements

View full text Add to dashboard Cite

show abstract

“…(II) which can be obtained from [C(NH 2 ) 3 ] + [SbCl 6 ] ! and PCl 5 [1] or from [C(N 3 ) 3 ] + [SbCl 6 ] ! and PCl 3 [2].…”

Section: Stable Tris(trichlorophosphoranylidenamino)carbenium Cation mentioning

confidence: 99%

Quantum-Chemical Investigation of Structure and Vibration Spectrum of [C(NPCl3)3]+ Cation

Semenov

Sigolaev

2005

Russ J Gen Chem

View full text Add to dashboard Cite

Structural parameters of the cation [C(NPCl 3 ) 3 ] + in vacuum and in acetonitrile are calculated by the methods RHF/6-311G(3d 6 ), RHF/6-31(3d 5 ) and B3LYP/6-311(3d 5 f 7 ). Formation energy of the free adduct (MeCN) 2[C(NPCl 3 ) 3 ] + is calculated and nonspecific character of interaction of the cation with liquid acetonitrile is established. Vibration spectrum of the cation is calculated and theoretical interpretation of IR and Raman spectra of the salt [C(NPCl 3 ) 3 ] + [SbCl 6 ] ! is refined. Stable tris(trichlorophosphoranylidenamino)carbenium cation (I) is a component of the soluble in acetonitrile salt [C(NPCl 3 ) 3 ] + [SbCl 6 ] ! (II) which can be obtained from [C(NH 2 ) 3 ] + [SbCl 6 ] ! and PCl 5 [1] or from [C(N 3 ) 3 ] + [SbCl 6 ] ! and PCl 3 [2]. It was es-tablished by X-ray structural investigation that in the crystal of II the cation I has almost symmetrical (C 3h ) structure with average bond lengths C3N 135, N3P 155, and P3Cl 196 pm [2,3].In this work we applied RHF/6-311G(3d 6 ), RHF/6-31(3d 5 ) and DFT B3LYP/6-311(3d 5 f 7 ) methods of GAUSSIAN [4] package for quantum-chemical investigation of structure of the cation I and of (MeCN) 2 (I) adduct both free (vac) and dissolved in acetonitrile (solv) (see Fig. 1). The nuclei of C, H, P and of three Cl atoms all fall to the symmetry plane xy of the cation I. Symmetry axes of acetonitrile moiety in the (MeCN) 2 (I) adduct coincide with the z axis. To account for the solvent effect (acetonitrile) we applied polarizable continuum model (C-PCM). (Table 1) depend only slightly on the used basis and the solvent reaction field value. Acetonitrile molecules contributing to (MeCN) 2 (I) solvatocomplex also show scarce effect. The C3N bond length is closer to that of C=N in methylimine (MeNCH 2 , 130 pm) rather than C3N in amines (Me 3 N 145 pm, Me 2 NH 146 pm, and MeNH 2 147 pm) [5]. Calculated bond lengths and bond anglesWe calculated IR spectrum of the cation I in the medium of acetonitrile by the method DFT B3LYP/6-311G(3d 5 f 7 ) without adjusting coefficients. Wave numbers and integral intensities of IR absorption are affected by solvent (Table 2), but the modes of normal vibration (Table 3) are insensitive.Comparing experimental IR and Raman spectra of the salt II with the spectra of related compounds, Mueller [3] noted extremely low frequency of nonsymmetrical bond vibration of phosphazene bonds which could not be explained satisfactorily and in his opinion it conforms hardly to experimental bond lengths. However, our calculation satisfactorily obeys both experimental bond lengths and vibration wave numbers of cation I. The maxima at 1003 and 1016 cm !1 in the IR spectrum or 1002 and 1013 cm !1 in the Raman spectrum are induced by vibration of the whole atomic group CN 3 P 3 rather than by assumed in Fig. 1. Equilibrium configuration of nuclei in the cation I(solv).

show abstract

Phosphazene. XIII. Cyclokondensation von Bis‐(trichlorphosphazo)‐methyl‐Kationen

Schmidpeter¹,

Böhm²

1968

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Die fünfgliedrige Kette eines Bis‐(trichlorphosphazo)‐methyl‐hexachloroantimonats kondensiert mit NH4Cl unter Ringschluß zum 3‐substituierten Tetrachlor‐diphosphatriazin VI, mit dem Hydrochlorid eines primären Amins zum 3,6‐disubstituierten Tetrachlordiphosphatriazinium‐hexachloroantimonat IV. Die 31P1H‐Kopplung in IV wird im Hinblick auf die Änderung der Winkel‐ und Bindungsverhältnisse beim Ringschluß diskutiert.

show abstract

Phosphazene. XII. Bis‐ und Tris‐ (trichlorphosphazo)‐methyl‐hexachloroantimonate

Cited by 7 publications

References 12 publications

Structural Chemistry of Non - Cyclic Phosphazenes

Structural Chemistry of Non - Cyclic Phosphazenes

Quantum-Chemical Investigation of Structure and Vibration Spectrum of [C(NPCl3)3]+ Cation

Phosphazene. XIII. Cyclokondensation von Bis‐(trichlorphosphazo)‐methyl‐Kationen

Contact Info

Product

Resources

About