Synthesis of alkali and alkaline earth metal complexes of open cryptands and their X-ray structures wherein M=Li+, Na+ and Ba2+

Syntheses are reported for the open cryptands (ROCH2CH2)(3)N (R=CH3, 1; C2H 5, 2) and their proton derivatives [H(ROCH2CH2)(3)N]X (R=CH3, X=Cl, 3; X=CF 3COO, 4; X=p-CH3C6H4COO, 5), alkali metal complexes, [M(ROCH2CH2)(3)N]X (M= Li, R=CH3, X=I, 6; X=ClO4, 7; R=C2H5, X=I, 10; M=Na, R=CH3, X=I, 8; X=ClO4, 9), alkaline earth metal complexes, {M[(ROCH2CH2)(3)N](2)}X-2 (M=Mg, R=CH3 , X=I, 11; X=ClO4, 12; R=C2H5, X=I, 18; M=Ca, R=CH3, X=I, 13; X=ClO4, 14; R =C2H5, X=I, 19; M=Sr, R=CH3, X=I, 15; R=C2H5, X=I, 20; M=Ba, R=CH3, X=I, 16 ; X=ClO4, 17; R=C2H5, X=I, 21), and alkaline earth hfac complexes, M(ROCH2C H2)(3)N(hfac)(2) (hfac =hexafluoroacetylacetonato, R=CH3, M=Mg, 22; M=Ca, 2 3; M=Ba, 24; R=C2H5, M=Mg, 25; M=Ca, 26; M=Ba, 27) are reported. The triest er [CH3OC(C=O)OCH2CH2](3)N, 28 was obtained in the course of this research. The characterizations of the open cryptands and their protonated derivativ es and complexes were performed by H-1, C-13 NMR, mass spectral and element al analysis. The structures of 3, 6, 8, 24 and 28 obtained by X-ray means a re also described. A structural feature of each of the complexes 6, 8 and 2 4 is the tetradentate coordination exhibited by the open cryptand. (C) 1999 Elsevier Science Ltd. All rights reserved.