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APPROACHES TO SELF-ASSEMBLED SYSTEMS BASED ON THE N-ACYLAMIDOPHOSPHATE COMPLEXES N. G. Zabirov 1, I. A. Litvinov 2 1 Kazan State University, E-mail: zabirov@mi.ru 2 Arbuzov Institute of Organic & Physical Chemistry
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X, Y = O, S (1) R: Alk; Ar; benzo-15-crown-5 (2) R: NR 2 R 3 ; NH-Z-NH; aza- and diaza-18-crown-6; aminobenzo-15- crown-5. Z: (CH 2 ) m m = 2-7; R 1 : OPr-i, OEt, Ph, OPh etc. [1] N. G. Zabirov et al. Uspechi khimii, 1991, 60, 2189; [2] R. M. Kamalov et al. Uspechi khimii, 1985, 54, 2044; [3] T. Q. Ly, J. D.Woollins, Coord. Chem. Rev., 1998, 176, 451. {2} (3)
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METHODS OF SYNTHESIS (1) (2)(2) {3} (4) (5)
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(6a) X = S (6b) X =O (6) (7) (7) R 1 = OPr-i {4}
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Trans-square M = Ni (II), Pd(II) Cis- square Pt (II) {Y=S}; M = Cu(II), Pd(II) {Y=O} Tetrahedron M = Co(II), Hg(II) {Y = S, O};Zn(II), Cd(II) {Y = S} (4) Zabirov N. G., Litvinov I. A., Kataeva O. N. et al. Russ.J.Gen.Chem. 1998, 1998, 9, 1408. (5) A.L.Kon’kin, V.G. Shtyrlin, N.G. Zabirov, I.A. Litvinov et al. Phosp. & Silicon 1999, 147, 449. R = Ph R 1 = OPr-i (8) C1-C2 9.6Å (9) C1-C2 8.0Å R = Ph R 1 = OPr-i {5}
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(Сo1), (Co2) N. G. Zabirov, F. D. Sokolov, V. V. Brusko, I. A. Litvinov, D. B. Krivolapov (unpublished work) R = Ph; R 1 = OPr-i (10) C1-C2 8.0Å (11) C1-C2 8.95Å {6}
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M M 1, M 2 M transition metal M 1, M 2 alkali metals {7} (13) (12) (14)
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M = Na +, K + Compound (16b) is soluble only in very polar solvents (H 2 O, DMSO, DMF). (16b) (a)(a)(a)(a) (c)(c)(c)(c) (b)(b)(b)(b) (15) {8}
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M = Ni(II), Pd(II), Co (II), Zn(II), Cd(II) M = Ni(II); R 1 : OPr-i; M. p. 125 ° C; 31 Р 50.0 ppm (17a) (a)(a)(a)(a) (17) (c)(c)(c)(c) (b)(b)(b)(b) (17a) 2HL + 2KOH 2LK + M 2+ ML 2 {9}
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{10} M = Zn(II); R: OPr-i; M. p. 114 ° C; 31 Р 53.8 ppm (18) CR: aza-18-crown-6
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M = Co (II), Ni (II), Pd (II), Cu (II), Zn(II), Cd(II), Hg(II) {11} (19) (20) (21) (22)
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R 1 = OPr-i {12} (23) 4.2 Å
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R 1 = OPr-i {13} (24)
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R 1 = OPr-i {14} (25)
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This work have been made due to support of Russian Foundation for Basic Research (grant # 00-03-32742a) and joint program of CRDF and Russian Ministry of Education «Basic Research and High Education” (grant REC-007). Dr. Dmitry B. Krivolapov A. E. Arbuzov Institute of Organic & Physical Chemistry Prof. Rafael A. Cherkasov Prof. Rafael A. Cherkasov Dr. Vasiliy V. Brusko Dr. Vasiliy V. Brusko Dr. Felix D. Sokolov Dr. Felix D. Sokolov Dr. Valery G. Shtyrlin Dr. Valery G. Shtyrlin Dr. Luisa N. Yamalieva Dr. Luisa N. Yamalieva Dr. Elvira G. Yarkova Dr. Elvira G. Yarkova Dr. Sergey V. Kashevarov Dr. Sergey V. Kashevarov Mr. Alexander Yu. Verat Mr. Alexander Yu. Verat Kazan State University Kazan State University ACKNOWLEDGEMENTS
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n = 1 X, Y = O, S n = 1, 2 X = S, Y = O,S n = 1- 4 X, Y = O Ia - group Na +, K +, Cs + Ib: Cu (I), Cu(II), Ag (I) f-elements: La -Yb, U IIb:Zn(II), Cd(II), Hg(II) VIIb: Mn(II) VIIIb: Co(II), Ni(II), Pd(II), Pt(II) Main group metals: IIIa Tl(I); IVa Sn(IV), Pb(II); Va Sb(III) (1, 2) (3)
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