Novel phosphazene derivatives: Synthesis, anisochronism and structural investigations of mono- and ditopic spiro-crypta phosphazenes
Date
2007Author
Asmafiliz, NuranIlter, Elif Ece
Isiklan, Muhammet
Kilic, Zeynel
Tercan, Baris
Caylak, Nagihan
Buyukgungor, Orhan
Metadata
Show full item recordAbstract
The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, with N2O2-donor type coronands (diaza-crown ethers) 1-3 afford novel monotopic 4-7 and ditopic 8-10 spiro-crypta phosphazenes, respectively. It has been observed that the reactions of N3P3Cl6 with I equivalent amount of coronands 1-3 yield only monotopic spiro-derivatives, while three equivalent amount of coronands 2 and 3 give dominantly ditopic dispiro-crypta-phosphazene skeletons. On the other hand, the P-31 NMR spectrum of 8 indicates that the ditopic spiro-ansa phosphazene 10 is present besides the ditopic dispiro derivative 8. Unexpectedly, the reaction of 6 with excess amount of pyrrolidine leads to the formation of geminal product 7. The P-31 NMR spectra of 4, 5, 6 and 10 indicate that all of these compounds have anisochronism. The structures of 5, 8 and 9 have been determined by X-ray crystallography. The relative radii of macrocyclic hole sizes of 5, 8 and 9 are calculated from the crystallographic results. The relationships between the exocyclic NPN and endocyclic NPN bond angles of the analogous compounds with delta P-shifts of NPN phosphorus atoms have been discussed. Thus, sums of the bond angles around the nitrogen atoms are in the range of [342.7(2)degrees-354.4(2)degrees], showing that the nitrogen atoms have pyramidal configurations. The pyramidal configuration gives rise to stereogenic properties. The salient spectroscopic features [FTIR, H-1, C-13, P-31 NMR, HETCOR (for 5 and 7) and MS] of all the compounds are presented. (c) 2006 Elsevier B.V. All rights reserved.
Source
Journal Of Molecular StructureVolume
832Issue
1-3Collections
Related items
Showing items related by title, author, creator and subject.
-
Phosphorus–nitrogen compounds. Part VI. Aminolysis of octachlorocyclotetraphosphazatetraene and the crystal structure of 2-trans-6-bis(n-propylamino)-2,4,4,6,8,8-hexakis-tert-butylaminocyclo-2λ5, 4λ5, 6λ5, 8λ5-tetraphosphazatetraene
Isiklan, M.; Kilic, Z.; Akduran, N.; Hokelek, T. (Elsevier Science Bv, 2003)The reactions of 2-trans-6-N4P4(NBPrn)(2)CI6 (2), which was obtained from N4P4Cl8 (1) and n-propylamine, with pyrrolidine and t-butylamine in different solvents have been studied. Compound (2) gave two different products, ... -
Phosphorus-nitrogen compounds. spiro- and crypta-phosphazene derivatives: Synthesis and spectral investigations. Structure of butane-N,N?-bis(1,4- oxybenzyl)-spiro(propane-1,3-diamino)tetrachlorocyclo-2?5, 4?5, 6?5-triphosphazatriene. Part VII
Ilter E.E.; Çaylak N.; Işiklan M.; Asmafiliz N.; Kiliç Z.; Hökelek T. (2004)The condensation reactions between trimer, N3P 3Cl6, and diamines, 2 and 4 and {1-{N-[1-(2- hydroxynaphthylmethyl)aminomethylidene]}-2(1H)-naphthalenone, 3, yielded the new spiro-cyclic- (5 and 8) and the novel spiro-phosphazene ... -
Phosphorus-nitrogen compounds. spiro- and crypta-phosphazene derivatives: synthesis and spectral investigations. Structure of butane- N, N'-bis(1,4-oxybenzyl)- spiro(propane-1,3-diamino)tetrachlorocyclo-2λ 5, 4λ 5, 6λ 5-triphosphazatriene. Part VII
Ilter, EE; Caylak, N; Isiklan, M; Asmafiliz, N; Kilic, Z; Hokelek, T (Elsevier, 2004)The condensation reactions between trimer, N3P3Cl6, and diamines, 2 and 4 and {1-{N-[1-(2-hydroxynaphthylmethyl)aminomethylidene]}-2(1H)-naphthalenone, 3, yielded the new spiro-cyclic- (5 and 8) and the novel spiro-phosphazene ...