Ion-Bearing Propellers: Alkali Metal Complexes of Tris(2-alkoxyphenyl)amine Ionophores

NMR spectroscopic studies reveal that binding of Na(+) by tris(2-methoxyphenyl)amine (3) brings two of these tripod ethers together about the metal ion; the related double-tripod-ether ionophore 1,2-bis[2-(bis(2-methoxyphenyl)amino)phenoxy]ethane (4), in which two triarylamines are covalently attached, binds LiI, LiBPh(4), NaI, NaBPh(4), and KB(4-ClPh)(4). Dynamic NMR puts lower limits on binding free energies of 4 for Na(+) (71.8 kJ mol(-)(1)) and K(+) (66.8 kJ mol(-)(1)) ions. X-ray studies of 3(2).NaBPh(4), 4.NaBPh(4), 4.NaB(4-ClPh)(4), and 4.KB(4-ClPh)(4).CH(3)NO(2) show eight-coordinate M(+) ions bound between crystallographically independent, homochiral triarylamine tripod ethers in structures reminiscent of alkali metal [2.2.2] cryptates. Complexes crystallize as follows: 3(2).NaBPh(4), monoclinic, P2(1)/c, Z = 4, a = 10.701(3) ?, b = 37.593(3) ?, c = 13.774(2) ?, and beta = 98.24(2) degrees; 4.NaBPh(4), triclinic, P&onemacr;, Z = 2, a = 12.157(1) ?, b = 14.811(1) ?, c = 15.860(2) ?, alpha = 105.400(8) degrees, beta = 91.594(9) degrees, and gamma = 95.354(8) degrees; 4.NaB(4-ClPh)(4), monoclinic, P2(1)/n, Z = 4, a = 13.652(5) ?, b = 18.75(1) ?, c = 22.805(5) ?, and beta = 92.21(5) degrees; 4.KB(4-ClPh)(4).CH(3)NO(2), monoclinic, Pn, Z = 2, a = 13.663(4) ?, b = 12.228(3) ?, c = 18.712(8) ?, and beta = 91.45(3) degrees. They show variable N-M-N angles; 3(2).NaBPh(4) is surprisingly bent ( angleN-Na-N = 154.5 degrees ), while the 4.M(+) complexes are normal: nearly linear for Na(+) ( angleN-Na-N = 178.6, 178.1 degrees ) and again bent with the larger K(+) ( angleN-K-N = 164.5 degrees ). Finally, free 4 is structurally similar to 3; it crystallizes in the triclinic space group P&onemacr;, with Z = 2, a = 8.068(1) ?, b = 14.599(2) ?, c = 16.475(3) ?, alpha = 115.43(1) degrees, beta = 92.51(1) degrees, and gamma = 90.40(1) degrees.