ChemInform Abstract: The Reactions of N3P3Cl6 and Related Compounds with Difunctional Reagents. Comparisons and Contrasts

Alkubaisi, Abdulla H.; Deutsch, W. Francis; Hursthouse, M. B.; Parkes, Harold G.; Shaw, L. S.; Shaw, Robert A.

doi:10.1002/chin.198711380

Cited by 5 publications

(6 citation statements)

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“…In this reaction, the formation of the fully pyrrolidinyl-substituted phosphazenes [N 3 P 3 (macrocycle)(C 4 H 7 N) 4 ] was expected, but the major products isolated were the partially pyrrolidinyl-substituted geminal phosphazene derivatives [N 3 P 3 (macrocycle)(C 4 H 7 N) 2 Cl 2 ], 26 and 27 . The chloride replacement reactions of phosphazene derivatives with pyrrolidine lead to the non-geminal reaction pathways and 11 , 12 , and 18 8a with excess pyrrolidine gave only fully pyrrolidinyl-substituted products.…”

Section: Resultsmentioning

confidence: 99%

Phosphorus−Nitrogen Compounds. Part 13. Syntheses, Crystal Structures, Spectroscopic, Stereogenic, and Anisochronic Properties of Novel Spiro-Ansa-Spiro-, Spiro-Bino-Spiro-, and Spiro-Crypta Phosphazene Derivatives

Bіlge¹,

Demiriz²,

Okumuş³

et al. 2006

Inorg. Chem.

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The condensation reactions of N2Ox (x = 2, 3) donor-type aminopodand (4) and dibenzo-diaza-crown ethers (5, 6, and 9) with hexachlorocyclotriphosphazatriene, N3P3Cl6, produce two kinds of partially substituted novel phosphazene derivatives, namely, spiro-bino-spiro- (19) and spiro-crypta (21, 22, and 25) phosphazenes. The partially substituted spiro-ansa-spiro-phosphazene (11) reacted with pyrrolidine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) give the corresponding new fully substituted phosphazenes (14 and 16). Unexpectedly, the reactions of 23 and 24 with pyrrolidine result in only geminal crypta phosphazenes (26 and 27). The solid-state structures of 16 and 22 have been determined by X-ray diffraction techniques. The relative inner hole-size of the macrocycle in the radii of 22 is 1.27 A. The relationship between the exocyclic NPN (alpha') and endocyclic (alpha) bond angles for spiro-crypta phosphazenes and exocyclic OPN (alpha') bond angles for spiro-ansa-spiro- and spiro-bino-spiro-phosphazenes with 31P NMR chemical shifts of NPN and OPN phosphorus atoms, respectively, have been investigated. The structures of 10, 14, 16, 19, 21, 22, and 25-27 have also been examined by FTIR, 1H, 13C, and 31P NMR, HETCOR, MS, and elemental analyses. The 31P NMR spectra of 10, 21, 22, and 25 indicate that the compounds have anisochrony. In compounds 16 and 22, the spirocyclic nitrogen atoms have pyramidal geometries resulting in stereogenic properties.

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Section: Resultsmentioning

confidence: 99%

Phosphorus−Nitrogen Compounds. Part 13. Syntheses, Crystal Structures, Spectroscopic, Stereogenic, and Anisochronic Properties of Novel Spiro-Ansa-Spiro-, Spiro-Bino-Spiro-, and Spiro-Crypta Phosphazene Derivatives

Bіlge¹,

Demiriz²,

Okumuş³

et al. 2006

Inorg. Chem.

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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 B Struct Sci

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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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“…Early crystallographic studies have provided evidence that cyclotriphosphazenes carrying two or more different substituents show signi®cant differences in bond lengths (Mani et al, 1965(Mani et al, , 1966Allen et al, 1969;Ahmed & Pollard, 1972;Ahmed & Gabe, 1975;Ahmed & Fortier, 1980) and later studies revealed trends in both bond lengths and angles, which could be related to a variety of different physical and chemical properties (Contractor et al, 1985;Fincham et al, 1986;Alkubaisi et al, 1988). It is known that substituent basicity constants give a reliable indication of the relative electronreleasing capacity of different substituent X groups (Feakins et al, 1965;Feakins, Last et al, 1969; and it was found that changes in bond lengths and angles of the series of cyclophosphazene derivatives (1a)±(1e) varied with the sum of the substituent basicity constants AE R (Bes Ëli et al, 2002).…”

Section: Discussionmentioning

confidence: 99%

Structural investigations of phosphorus–nitrogen compounds. 6. Relationships between molecular parameters in per-X-substituted bridged spermine derivatives and basicity constants ΣαR of substituents

Coles

Davies

Hursthouse

et al. 2004

Acta Crystallogr Sect B

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A systematic study is reported of the products of the nucleophilic substitution reactions of the spermine-bridged cyclotriphosphazene, [N 3 t , respectively. A comparison has been made between the sum of the substituent basicity constants, AE R , obtained in nitrobenzene solution, and ten molecular parameters of the N 3 P 3 ring (the internal bond angles , , , and , and the PÐN bond lengths a, b, c, d and e) as well as the difference between the bond lengths a and b, Á(PÐN). It is found that the systematic change in molecular parameters of compounds (2a)±(2g) is in line with changes in R values, indicating the similarity in relative electronreleasing capacity of substituents X in the solid state and in solution. It is also found that the effect on molecular parameters of (2a)±(2g) with two X substituents in PX 2 groups is greater than that for one X substituent in P(OR)X groups in an analogous series of compounds observed previously . Acta Cryst. B58, 1067±1073].

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ChemInform Abstract: The Reactions of N3P3Cl6 and Related Compounds with Difunctional Reagents. Comparisons and Contrasts

Cited by 5 publications

References 1 publication

Phosphorus−Nitrogen Compounds. Part 13. Syntheses, Crystal Structures, Spectroscopic, Stereogenic, and Anisochronic Properties of Novel Spiro-Ansa-Spiro-, Spiro-Bino-Spiro-, and Spiro-Crypta Phosphazene Derivatives

Phosphorus−Nitrogen Compounds. Part 13. Syntheses, Crystal Structures, Spectroscopic, Stereogenic, and Anisochronic Properties of Novel Spiro-Ansa-Spiro-, Spiro-Bino-Spiro-, and Spiro-Crypta Phosphazene 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. 6. Relationships between molecular parameters in per-X-substituted bridged spermine derivatives and basicity constants ΣαR of substituents

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ChemInform Abstract: The Reactions of N3P3Cl6 and Related Compounds with Difunctional Reagents. Comparisons and Contrasts

Cited by 5 publications

References 1 publication

Phosphorus−Nitrogen Compounds. Part 13. Syntheses, Crystal Structures, Spectroscopic, Stereogenic, and Anisochronic Properties of Novel Spiro-Ansa-Spiro-, Spiro-Bino-Spiro-, and Spiro-Crypta Phosphazene Derivatives

Phosphorus−Nitrogen Compounds. Part 13. Syntheses, Crystal Structures, Spectroscopic, Stereogenic, and Anisochronic Properties of Novel Spiro-Ansa-Spiro-, Spiro-Bino-Spiro-, and Spiro-Crypta Phosphazene 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. 6. Relationships between molecular parameters in per-X-substituted bridged spermine derivatives and basicity constants ΣαR of substituents

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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