No abstract

A series of 1,1 0 -binaphthalene-2,2 0 -diyl phosphate (BNPPA À ) salts have been synthesized. Their crystal packings show a separation of the hydrophobic naphthyl and hydrophilic (RO) 2 PO 2 À phosphate/cation/solvate regions. Hydrogen bonding in the latter is the driving force for ''inverse bilayer'' formation, with a hydrophilic interior exposing the hydrophobic binaphthyl groups to the exterior. Stacking of the inverse bilayers occurs less through p-p and more through CHÁ Á Áp interactions between the naphthyl groups, which correlates with the formation of thin crystal plates along the stacking direction. Cations used with R-or rac-BNPPA À are protonated isonicotin-1-ium amide (1), isonicotin-1-ium acid (2), guanidinium (3), the metal complexes transtetraammine-dimethanol-copper(II) (4), trans-diaqua-tetramethanol-copper(II) (5) and cis-diaquabis(ethylene diamine)-nickel(II) (6). Crystallization occurs with inclusion of water and methanol solvent molecules, except in 2. Starting from R-BNPPA, inversion takes place with calcium acetate to give 1 as the racemate. 2 is crystallized as the R-BNPPA salt. The inversionsymmetrical complex trans-[Cu(H 2 O) 2 (CH 3 OH) 4 ] 21 in 5 has Cu-OH 2 bond lengths of 1.937(4) A ˚, and Cu-O(methanol) of 2.112(4) and 2.167(4) A ˚, corresponding to a compressed tetragonal geometry.Scheme 1 Molecules with a polar head (J) and a non-polar tail (Q) can spontaneously form (a) monolayers, (b) micelles, (c) bilayers and (d) liposome vesicles.

Nuclear inelastic scattering (NIS) measurements were performed on a guanidium nitroprusside ((CN(3)H(6))(2)[Fe(CN)(5)NO], GNP) monocrystal at 77 K after the sample was illuminated with blue light (450 nm) at 50 K to populate the two metastable states, MS(1) and MS(2), of the nitroprusside anion. A second measurement was performed at 77 K after warming up the illuminated crystal to 250 K where the metastable states decay to the groundstate. The measured spectra were compared with simulated NIS spectra that were calculated by using density functional methods. Comparison of measured and simulated spectra provides strong evidence for the isonitrosyl structure of the metastable MS(1) state proposed by Carducci et al. (Carducci, M. D.; Pressprich, M. R.; Coppens, P. J. Am. Chem. Soc. 1997, 119, 2669-2678).

Ag(isonicotinamide) 2 NO 3 ] 2 , featuring a short Ag· · ·Ag contact and a strong hydrogen-bonding network in the solid state, is a light-stable and still readily soluble form of silver nitrate, showing little complex formation in solution but a counter-intuitive decrease in dissolution rate with decrease of pH.

A high-yield, mmolar-scale synthesis of pure guanidinium nitroprusside, (CN 3 H 6 ) 2 [ (57) Fe(CN) 5 NO] (GNP) from iron metal is described. The iron metal contained pieces of 95.3% 57 Fe together with normal iron so that an isotope enrichment in 57 Fe of 25% was achieved. Single-crystals of GNP could be grown in cubic shape and dimensions of about 3´4´4 mm 3 . The purity of the GNP product and the intermediates K 4 [ (57) Fe(CN) 6 ]´3 H 2 O and Na 2 [ (57) Fe-(CN) 5 NO]´2 H 2 O was ascertained by 57 Fe Mo È ssbauer spectroscopy as well as 13 C, 14 N and 57 Fe NMR spectroscopy. The 57 Fe NMR chemical shift for [ (57) Fe(CN) 5 NO] 2± in GNP was detected at +2004.0 ppm [vs Fe(CO) 5 ]. Synthese von Isotopen-angereichertem (CN 3 H 6 ) 2 [ 57 Fe(CN) 5 NO] ausgehend von 57 Fe Inhaltsu È bersicht. Es wird eine Synthese mit hoher Ausbeute und im mmol-Bereich von reinem Guanidiniumnitroprussiat, (CN 3 H 6 ) 2 [ (57) Fe(CN) 5 NO] (GNP) ausgehend von Eisenmetall beschrieben. Das Eisenmetall enthielt Stu È cke von 95.3%-igem 57 Fe und normales Eisen, so dass eine Isotopenanreicherung in 57 Fe von 25% erreicht wurde. Einkristalle von GNP konnten als Quader mit Abmessungen von etwa 3´4´4 mm 3 gezu È chtet werden. Die Reinheit des GNP-Produktes und der Zwischenprodukte K 4 [ (57) Fe(CN) 6 ]´3 H 2 O und Na 2 [ (57) Fe(CN) 5 NO]´2 H 2 O wurde mittels 57 Fe Mo È ssbauer Spektroskopie und fu È r K 4 [ (57) Fe(CN) 6 ]´3 H 2 O auch mit 13 C, 14 N and 57 Fe NMR Spektroskopie u È berpru È ft. Die 57 Fe NMR chemische Verschiebung fu È r [ (57) Fe(CN) 5 NO] 2± in GNP wurde bei +2004.0 ppm [vs Fe(CO) 5 ] detektiert.