X-ray crystallography of the Cl3[N(CH3)2]3P3N3 compounds. III. trans Nongeminal 2,4,6-trichloro-2,4,6-trisdimethylaminocyclotriphosphazatriene

Ahmed, F.R.; Gabe, E. J.

doi:10.1107/s0567740875004438

Cited by 17 publications

(12 citation statements)

References 6 publications

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“…The non-geminal P-Cl bond, d 0 , is longer than the corresponding bond lengths, d, of the PCl 2 group. The opposite behaviour is observed for the exocyclic P-N bond length e 0 , which is substantially shorter than those in geminal groups, e. Both effects have been observed in similar structures (Ahmed & Pollard, 1972;Ahmed & Gabe, 1975;Ahmed & Fortier, 1980;Alkubaisi et al, 1988;Beşli, Coles, Davies, Hursthouse, Kilic, Mayer, Shaw & Yenilmez, 2002;Coles, Davies, Eaton et al, 2004;Beşli, Coles, Davies, Eaton et al, 2004). The sum of the bond angles around the exocyclic N atom [358.3 (1) ] shows that it has trigonal planar character.…”

Section: Molecular Structuresmentioning

confidence: 92%

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N₃P₃Cl_{(6 − n)}(NHBu^t)_n derivatives

Bartlett

Coles

Davies

et al. 2006

Acta Crystallogr Sect B

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A series of compounds of the N 3 P 3 Cl (6 À n) (NHBu t ) n family (where n = 0, 1, 2, 4 and 6) are presented, and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N 3 P 3 Cl 5 (NHBu t ) and N 3 P 3 Cl 2 (NHBu t ) 4 have been determined at 120 K, and those of N 3 P 3 Cl 6 and N 3 P 3 Cl 4 (NHBu t ) 2 have been redetermined at 120 K. These are compared with the known structure of N 3 P 3 (NHBu t ) 6 studied at 150 K. Trends in molecular parameters [phosphazene ring, P-Cl and P-N(HBu t ) distances, PCl 2 angles, and endo-and exocyclic phosphazene ring parameters] across the series are observed. Hydrogen-bonding motifs are identified, characterized and compared. Both the molecular and the hydrogen-bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBu t ) group.

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Section: Molecular Structuresmentioning

confidence: 92%

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N₃P₃Cl_{(6 − n)}(NHBu^t)_n derivatives

Bartlett

Coles

Davies

et al. 2006

Acta Crystallogr Sect B

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“…By contrast, the mean exocyclic P-N bond lengths in PCI(NRR') moieties are shorter. In cis-N3P3(NMe2)2CI4, trans-N3P3(NMe2)3Cl3 (Ahmed & Fortier, 1980), geminal N3P3(NMe2)3C13 (Ahmed & Pollard, 1972a), cis-N3P3(NMe2)3C13 (Ahmed & Pollard, 1972b), and trans-N3P3(NMe2)2Cl 4 (Ahmed & Gabe, 1975), they are 1.617 (4), 1.615 (4), 1.628 (4), 1.610 (4) and 1.623 (2)A respectively. However, in geminal N3P3(NH2)2F4 (Pohl & Krebs, 1976) (effect of F substituents) and geminal N3P3(NHPri)4CI>HCI (Mani & Wagner, 1971) (effect of protonation) the mean exocyclic P-N bond lengths are only 1.602 (4) and 1.609 (3)A respectively.…”

Section: Introductionmentioning

confidence: 99%

Structural investigations of phosphorus–nitrogen compounds. 2. The structures of N₃P₃(NH₂)₂Cl₄, N₃P₃(NPPh₃)(NH₂)Cl₄ and N₃P₃(NPPh₃)Cl₅ and a comparison with other phosphazenylphosphazenes. The relationship of conformation in the solid state to conformation in solution

Fincham¹,

Hursthouse²,

Parkes³

et al. 1986

Acta Crystallogr Sect B

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The crystal structures of 2,2-diamino-4,4,6,6-tetrachlorocyclotriphosphazatriene, N3P3(NH2)2C14 (1), and of 2-amino-2-triphenylphosphazenyl-4,4,6,6-tetrachlorocyclotriphosphazatriene, N3P3(NPPh3)-(NH2)C14 (2), have been determined and that of 2-triphenylphosphazenyl-2,4,4,6,6-pentachlorocyclotriphosphaz~:riene, N3P3(NPPh3)C15 (3), has been redeterminc,l by X-ray analysis. [Crystal data: For compound (1) the presence of geminal NH2 groups is established. Compound (2) is the first triphenylphosphazenyl derivative with a type III conformation, and compound (3) has a type I conformation. Structures are compared with those of related compounds. The relationship between conformation in the solid state as determined by dihedreal angles of the phosphazenyl substituent relative to the ring and the preferred conformations in solution as measured by 4j(pp) spin-spin coupling constants is discussed.

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“…The molecule lies on a crystallographic twofold rotation axis. A comparison of corresponding bond lengths with literature data (Allen et al, 1988;Ahmed & Gabe, 1975, Ahmed & Fortier, 1980 shows that there is no significant difference in the length of either the exocyclic P-Cl bond or the P-N(Me) bond. However, a remarkable deviation was found in the P-N bond distances of the P 3 N 3 ring.…”

Section: Commentmentioning

confidence: 78%

“…Many crystal structures of amido derivatives of chlorophosphazenes have been reported (e.g. Polder & Wagner, 1976;Bartlett et al, 2006;Ahmed & Gabe, 1975, Ahmed & Fortier, 1980. Compound (I) is the first trans non-geminal tetrasubstituted derivative of this class of compounds to be structurally characterized (Fig.…”

Section: Commentmentioning

confidence: 99%

trans-2,6-Dichloro-2,4,4,6-tetrakis[methyl(trimethylsilyl)amino]-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphorine

et al. 2007

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X-ray crystallography of the Cl₃[N(CH₃)₂]₃P₃N₃ compounds. III. trans Nongeminal 2,4,6-trichloro-2,4,6-trisdimethylaminocyclotriphosphazatriene

Cited by 17 publications

References 6 publications

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N₃P₃Cl_{(6 − n)}(NHBu^t)_n derivatives

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N₃P₃Cl_{(6 − n)}(NHBu^t)_n derivatives

Structural investigations of phosphorus–nitrogen compounds. 2. The structures of N₃P₃(NH₂)₂Cl₄, N₃P₃(NPPh₃)(NH₂)Cl₄ and N₃P₃(NPPh₃)Cl₅ and a comparison with other phosphazenylphosphazenes. The relationship of conformation in the solid state to conformation in solution

trans-2,6-Dichloro-2,4,4,6-tetrakis[methyl(trimethylsilyl)amino]-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphorine

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X-ray crystallography of the Cl3[N(CH3)2]3P3N3 compounds. III. trans Nongeminal 2,4,6-trichloro-2,4,6-trisdimethylaminocyclotriphosphazatriene

Cited by 17 publications

References 6 publications

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 − n)(NHBu t ) n derivatives

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 − n)(NHBu t ) n derivatives

Structural investigations of phosphorus–nitrogen compounds. 2. The structures of N3P3(NH2)2Cl4, N3P3(NPPh3)(NH2)Cl4 and N3P3(NPPh3)Cl5 and a comparison with other phosphazenylphosphazenes. The relationship of conformation in the solid state to conformation in solution

trans-2,6-Dichloro-2,4,4,6-tetrakis[methyl(trimethylsilyl)amino]-1,3,5,2λ5,4λ5,6λ5-triazatriphosphorine

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X-ray crystallography of the Cl₃[N(CH₃)₂]₃P₃N₃ compounds. III. trans Nongeminal 2,4,6-trichloro-2,4,6-trisdimethylaminocyclotriphosphazatriene

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N₃P₃Cl_{(6 − n)}(NHBu^t)_n derivatives

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N₃P₃Cl_{(6 − n)}(NHBu^t)_n derivatives

Structural investigations of phosphorus–nitrogen compounds. 2. The structures of N₃P₃(NH₂)₂Cl₄, N₃P₃(NPPh₃)(NH₂)Cl₄ and N₃P₃(NPPh₃)Cl₅ and a comparison with other phosphazenylphosphazenes. The relationship of conformation in the solid state to conformation in solution

trans-2,6-Dichloro-2,4,4,6-tetrakis[methyl(trimethylsilyl)amino]-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphorine