Nucleophilic substitution reactions of monofunctional nucleophilic reagents with cyclotriphosphazenes containing 2,2-dioxybiphenyl units.

The nucleophilic substitution reactions of mono- and bis-spiro-2,2' -dioxybiphenyl cyclotriphosphazenes (3 and 4) with cyclopropanemethylamine (5) and aniline (6) were performed in the presence of trimethylamine in THF. Five novel cyclopropanemethylamino- and anilino-substituted spiro-2,2' -dioxybiphenyl cyclotriphosphazene derivatives (7-11) were obtained from these reactions. The molecular structures of the new cyclotriphosphazene derivatives (7-11) were characterized by elemental analysis, MALDI-TOF MS, FT-IR, and NMR ( P and H) spectroscopies.

Synthesis, characterization and oxygen sensitivity of cyclophosphazene equipped-iridium (III) complexes.

In this work, synthesis, characterization and oxygen sensing abilities of the cyclophosphazene-free and phenyl and naphtoxy-substituted cyclophosphazene bearing iridium (III) complexes (Ir-I, Ir-II and Ir-III) were presented. The complexes were characterized by NMR, absorption and emission spectroscopies, luminescence lifetime and quantum yield measurements. The molecules were successfully embedded in the ethyl cellulose matrix to fabricate the oxygen sensing electrospun mats via electrospinning technique.

Synthesis of a new class of fused cyclotetraphosphazene ring systems.

Octachlorocyclotetraphosphazene (1) was reacted with butylamines [n-butyl, i-butyl, sec-butyl, and t-butyl] in a 1:0.8 mol ratio in THF to obtain cyclotetraphosphazenes bearing a P-NH group, N4P4Cl7(NHR) [R = n-butyl (2a), i-butyl (2b), sec-butyl (2c), t-butyl (2d)](2a-d). The cyclotetraphosphazene derivatives 2a, 2b, and 2c were treated with sodium hydride giving rise to a new type of cyclophosphazene compounds (P8N8 ring) consisting of three fused tetramer rings (3a-c).

The diverse behaviour of the P-Cl bonds in the spiro-cis-ansa spermidine derivative cyclotriphosphazene towards mono-functional nucleophilic reagents.

A number of new spiro-ansa spermidine derivative cyclotriphosphazenes (2-10) is synthesized in order to provide insight into the reaction mechanism for nucleophilic substitution. The structures of the compounds were determined by elemental analysis, mass (MS), (1)H, (19)F (for 9) and (31)P NMR spectroscopies. Compounds (2-8) and 9, 10 can be formed by a proton abstraction-chloride elimination and both the S(N)(1) and S(N)(2) reaction mechanisms, respectively.

Dimorphism in 4,4,6,6-tetrachloro-2,2-(2,2-dimethylpropane-1,3-dioxy)cyclotriphosphazene and 6,6-dichloro-2,2:4,4-bis(2,2-dimethylpropane-1,3-dioxy)cyclotriphosphazene.

A second, polymorphic, form of the previously reported compound 4,4,6,6-tetrachloro-2,2-(2,2-dimethylpropane-1,3-dioxy)cyclotriphosphazene, C(5)H(10)Cl(4)N(3)O(2)P(3), is now reported. The molecular structures of these two compounds are similar, aside from minor conformational differences. However, the compounds crystallize in two different space groups and exhibit quite different crystal structure assemblies.

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.

A series of compounds of the N3P3Cl(6 - 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 N3P3Cl5(NHBu(t)) and N3P3Cl2(NHBu(t))4 have been determined at 120 K, and those of N3P3Cl6 and N3P3Cl4(NHBu(t))2 have been redetermined at 120 K. These are compared with the known structure of N3P3(NHBu(t))6 studied at 150 K.

Retention of configuration in the nucleophilic substitution reactions of some nine-membered ansa derivatives of cyclotriphosphazatriene.

X-ray crystallographic evidence shows that nucleophilic substitution reactions of two different types of cyclophosphazene derivatives with relatively rigid nine-membered ansa rings leads to the first demonstration of retention of configuration in these molecular systems.

Conformational polymorphism in a chiral spiro-cis-ansa-bridged cyclotriphosphazene derivative.

The reaction of spermidine with 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazene produces a mixture of products of which one of the fractions is a spiro-cis-ansa derivative, namely 12-chloro-14,14-diphenyl-2,6,11,13,15,16-hexaaza-1,12-diphosphatricyclo[10.3.1.