Akademik Veri Yönetim Sistemi
Journal of Inclusion Phenomena and Macrocyclic Chemistry, cilt.65, sa.3, ss.269-286, 2009 (SCI-Expanded)
The condensation reactions of N2O3-donor type coronands (1-3) with hexachlorocyclotriphosphazatriene, N3P3Cl6, resulted in the formation of spiro-crypta phosphazene derivatives (4-6). These compounds with excess morpholine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) afford fully substituted morpholino (7 and 10) and 1,4-dioxa-8-azaspiro[4,5]deca (8)-substituted phosphazene derivatives, respectively. Whilst, in the same conditions, the reactions of 4, 5 and 6 with pyrrolidine, morpholine and DASD also produce partially pyrrolidino-substituted geminal (9 and 11), mono-substituted pyrrolidino (12), morpholino (13) and 1,4-dioxa-8-azaspiro[4,5]deca (14) phosphazenes. It has been clearly observed that the chloride replacement reactions of 4, 5 and 6 with pyrrolidine lead to the geminal products. Compounds 7, 8 and 10 are the first examples of anisochronic tetrakis (amino) phosphazenes according to 31P NMR data. The structures of 7, 8 and 10-14 have been determined by FTIR, MS, 1H, 13C and 31P NMR, DEPT, and HETCOR spectral data. The solid-state structures of 9, 13 and 14 have been examined by X-ray diffraction techniques. The sums of the bond angles around the spiro cyclic nitrogen atoms [344.8(4)° and 347.6(4)°] of 9, indicate that the nitrogen atoms have pyramidal geometries. Thus, the N atoms seem to have stereogenic configurations. Compounds 12-14 also have two stereogenic P-atoms, and they are expected to be in the mixture of enantiomers. The relationships between NPN (α and α′) bond angles and δPspiro values and the correlation of Δ(P-N) with δPspiro and Δ(δP) values are presented. © Springer Science+Business Media B.V. 2009.