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DOI: 10.1039/A708245B (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 1489-1498

Complexation of phosphoryl-containing mono-, bi- and tri-podands with alkali cations in acetonitrile. Structure of the complexes and binding selectivity

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Vitaly P. Solov’ev, Vladimir E. Baulin, Nadezhda N. Strakhova, Vladimir P. Kazachenko, Vitaly K. Belsky, Alexandre A. Varnek, Tatiana A. Volkova and Georges Wipff

Abstract

We present experimental and theoretical studies on new ionophores (L) which possess a high complexation ability for Li+ or Na+ cations. Four tri-podands (R1–O–C2H4–)3N [R1 = –CH2–P(O)Ph2 (P1), –C2H4– P(O)Ph2 (P2), -o-C6H4P(O)Ph2 (P3) and -o-C6H4–CH2–P(O)Ph2 (P4)], one bi-podand (R2–O–C2H4–)2N–CH3 [R2 = -o-C6H4–CH2–P(O)Ph2 (P5)] and one mono-podand [R2–O–(CH2–CH2–O)3–R2 (P6)] containing phosphine oxide terminal groups have been synthesised. Stability constants, enthalpies and entropies of their complexation with lithium, sodium and potassium thiocyanates have been determined in acetonitrile at 298 K by a calorimetric titration technique. We find that tri-podands form a variety of complexes [(M+)3L, (M+)2L, M+L and M+L2)], whereas the bi- and mono-podand form only M+L complexes with Li+ and Na+, and M+L and M+L2 complexes with K+. Formation of poly-nuclear (M+)nL complexes of tri-podands in solution has been confirmed by electro-spray mass spectrometry. At relatively small concentrations of the ligand (C[hair space] 0L), P1 binds Na+ much better than Li+, whereas P4 and P5 display a remarkable Li+/Na+ selectivity; at large C0L the complexation selectivity decreases. X-Ray diffraction studies performed on monocrystals of complexes of NaNCS with tri-podands P2 and P3 show that Na+ is encapsulated inside a ‘basket-like’ pseudocavity, coordinating all donor atoms of the tri-podand. Molecular dynamics simulations on P2, P3 and P4 and on their 1∶1 complexes with M+ in acetonitrile solution suggest that the structures of M+L complexes in solution are similar to those found for P2 and P3 complexes in the solid state.

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