Preparation, Spectroscopic and Structural Investigations of Spiro Derivatives of Hexachlorocyclotriphosphazatriene

Contractor, Sorab R.; Hursthouse, Michael B.; Parkes, Harold G.; Shaw, L. S.; Shaw, Robert A.; Yılmaz, H.

doi:10.1080/03086648308075989

Cited by 10 publications

(4 citation statements)

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“…The molecular structure of the di-monoansa compound 6 in Figure 2 is that of a symmetrically-bridged spermine derivative, where the cyclophosphazene substituents both possess a propanedioxy ansa-bridged moiety, giving rise to a centrosymmetric structure with the centre of inversion about the central C-C bond of the spermine bridge. The cyclophosphazene ring is heavily distorted, as observed in similar ansa-bridged examples [18], with a maximum deviation from the mean ring plane of 0.328Å for the nitrogen atom (N1) bridged by the ansa group. This give rise to compression of the cyclophosphazene ring, where the non bonded P…P separation between atoms P1 and P2 is 2.615Å.…”

Section: Formation Of Spiro-and Ansa-substituted Spermine-bridged Cycmentioning

confidence: 88%

Structural and stereogenic properties of spiro- and ansa-substituted 1,3-propanedioxy derivatives of a spermine-bridged cyclotriphosphazene

et al. 2006

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Reaction of 1,3-propanediol with the achiral spermine-bridged cyclophosphazene 1 at various molar ratios in THF gives a number of spiro-and ansa-derivatives that exhibit different stereogenic properties, viz. racemic, meso or achiral forms. As expected, spiro forms are preferred (giving mono-, di-, tri-and tetra-substitution), although significant amounts of mono-and di-substituted ansa derivatives also occur. A number of new structures have been characterized by NMR spectroscopy and X-ray crystallography in this work; mono-spiro 2, di-mono-ansa 6 and di-spiro/mono-ansa 8. The mono-ansa compound 3 was observed in solution by NMR spectroscopy but no evidence was found for the monospiro/monoansa 5, a necessary precursor of compound 8. The tri-spiro derivative 7 has been isolated and characterized by 31 P NMR spectroscopy, whereas the structures of the di-monospiro 4 (meso) and tetra-spiro 9 have been characterized previously. The stereogenic properties of many of the products have been confirmed by X-ray crystallography and/or by 31 P NMR spectroscopy on addition of the chiral solvating agent, (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol.Although the starting compound 1 is achiral, it is found that unsymmetrically-substituted derivatives with 1,3-propanediol give racemic mixtures for the mono-spiro 2 and tri-spiro 7 derivatives, whereas symmetrically-substituted derivatives such as di-mono-ansa 6 and dispiro/mono-ansa 8 are meso. It is found that care must taken in interpreting the 'splitting' of 31 P NMR signals on addition of CSA in terms of 'chirality' of molecules, because some meso compounds give false positive results due to changes from A 2 X-like to A 2 B or ABX spin systems.

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Section: Formation Of Spiro-and Ansa-substituted Spermine-bridged Cycmentioning

confidence: 88%

Structural and stereogenic properties of spiro- and ansa-substituted 1,3-propanedioxy derivatives of a spermine-bridged cyclotriphosphazene

et al. 2006

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“…Compound 2 was prepared as in the literature [ 4 ], characterised by 1 H and 31 P NMR [ 5 ] and was crystallised from dichloromethane. The melting temperature of compound 2 in the literature [ 1 ] is given as 429–430 K but is measured as 427 K by Differential Scanning Calorimetry (DSC) in this work.…”

Section: Methodsmentioning

confidence: 99%

Characterisation of temperature-dependent phase transitions in 2,2-trimethylenedioxy- 4,4,6,6-tetrachlorocyclotriphosphazene, N3P3Cl4[O(CH2)3O]

Coles

Davies

Hursthouse

et al. 2007

Chemistry Central Journal

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Background: The crystal structure of 2,2-trimethylenedioxy-4,4,6,6-tetrachlorocyclo triphosphazene has been determined at 120, 274 and 293 K. The result at 293 K confirms the room temperature Cmc2 1 structure, but at the lower temperatures the space group is Pna2 1 . Nevertheless the basic structure remains the same, with only small displacements of the atoms, amounting to an average of 25 pm between 120 and 293 K.

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“…A similar configuration is observed for other bridged cyclotriphosphazene derivatives. 35 Comparison of the data reveals that there seems to be a relationship between the length of the loop and the deviation of the nitrogen atom enclosed by the bridged P atoms from the plane of the remaining ring atoms. For instance, for the molecules 6-8 this deviation is 0.4 Å for 7, whereas the inorganic ring of 8 shows no significant deviation from planarity.…”

Section: Crystal Structure Of Compoundmentioning

confidence: 98%

“…For instance, for the molecules 6-8 this deviation is 0.4 Å for 7, whereas the inorganic ring of 8 shows no significant deviation from planarity. 35,36 The compression of the inorganic ring is also reflected by the contraction of the non-bonded P ؒ ؒ ؒ P distances (y, yЈ, yЉ). In (NPCl 2 ) 3 this distance is 2.746(2) Å while for compound 6 y has a normal value of 2.7508(9) Å, yЈ is shortened to 2.716(1) Å and yЉ is even further reduced to 2.6750(9) Å.…”

Section: Crystal Structure Of Compoundmentioning

confidence: 99%

A propene-substituted cyclotriphosphazene: synthesis, characterization and polymerization

Bosscher¹,

Meetsma²,

Vandegrampel³

1997

J. Chem. Soc., Dalton Trans.

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Preparation, Spectroscopic and Structural Investigations of Spiro Derivatives of Hexachlorocyclotriphosphazatriene

Cited by 10 publications

References 0 publications

Structural and stereogenic properties of spiro- and ansa-substituted 1,3-propanedioxy derivatives of a spermine-bridged cyclotriphosphazene

Structural and stereogenic properties of spiro- and ansa-substituted 1,3-propanedioxy derivatives of a spermine-bridged cyclotriphosphazene

Characterisation of temperature-dependent phase transitions in 2,2-trimethylenedioxy- 4,4,6,6-tetrachlorocyclotriphosphazene, N3P3Cl4[O(CH2)3O]

A propene-substituted cyclotriphosphazene: synthesis, characterization and polymerization

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