SYNTHESIS AND PROPERTIES OF CROWN ETHER-ALKALI METAL CATION INTERCALATION COMPOUNDS OF MPS3 (M = MN, CD, ZN)

The crown ether-alkali metal cation intercalation compounds (15-crown-5)0.33K0.4Mn0.8PS3 (4), (15-crown-5)0.43K0.5-Cd0.75PS3.H2O (5), (15-crown-5)0.3Na0.5Zn0.75PS3.H2O (6), (15-crown-5)0.43K0.3Na0.2Cd0.75PS3.H2O (7a-b), and the new cationic ionophore [CpRu(benzo-15-crown-5)]PF6 (1, Cp = eta5-C5H5) and its derivatives [CpRu(benzo-15-crown-5)]Cl (2), [CpRu(benzo-15-crown-5)(NaPF6)]BPh4 (21), and [CpRu(benzo-15-crown-5)(NaPF6)]PF6 (22) are described. Ion-exchange intercalation of 1 gave [CpRu(benzo-15-crown-5)]0.23Na0.4Mn0.7PS3.H2O (8), [CpRu(benzo-15-crown-5)]0.28(Me4N)0.02Mn0.85PS3.H2O (9), [CpRu(benzo-15-crown-5)]0.27Na0.5Cd0.6PS3-H2O (10), and[CpRu(benzo-15-crown-5)]0.34Na0.1Zn0.8PS3.H2O(11). The intercalates [CpFe(C6Me6)]0.28Cd0.6Na0.5PS3.H2O (12) and related materials containing [CpRu(p-cymene)] + (p-cymene = 4-isopropyltoluene), [CpFe(o-C6H4Cl2)]+, and [Cp*Ru(C6H6)]+ (CP* = eta5-C5Me5) intercalated into MnPS3 and CdPS3 have been prepared, and X-ray powder diffraction suggests that in this series the metal sandwich compounds' principal axes are parallel to the layer planes of the host lattice. Binding of Na+ by 1 in CD3CN and by 2 in D2O has been studied by C-13 and Na-23 NMR spectroscopy. The crystal structure of 21 [C43H45BF6NaOsPRu, monoclinic, P2(1)/c, a = 9.039(1) angstrom, b = 14.543(l) angstrom, c = 31.365(4) angstrom, beta = 96.61(l)-degrees, Z = 4, R = 0.042) confirms crown ether-Na+ complexation and includes an unusual eta2-coordination of PF6- to the sodium ion. A solid-state Na-23 NMR study of intercalates 6, 7a-b, and 10-12 suggests that sodium cations in these intercalates exist in several possible environments.