The reaction between ZnO and molten Na2S2O7 or K2S2O7 forming Na2Zn(SO4)2 orK2Zn(SO4)2, studied by Raman spectroscopy and x-ray diffraction.

Reactions between solid zinc oxide and molten sodium or potassium pyrosulfates at 500 degrees C are shown by Raman spectroscopy to be 1:1 reactions leading to solutions. By lowering the temperature of the solution melts, colorless crystals form. Raman spectra of the crystals are given and tentatively assigned.

4-metalated condensed pyrimidines: their preparation and reaction with aldehydes under Barbier-type conditions.

[reaction: see text] The organometallic intermediate obtained from halogen-metal exchanges of 4-iodo-6-phenylthieno[2,3-d]pyrimidine under Barbier-type conditions was reacted with aldehydes to form the corresponding alcohols in moderate yields. The reaction involving an organolithium intermediate proceeded only at low temperature, whereas the reaction involving a magnesium ate intermediate also proceeded at room temperature. A crystal structure confirms that the expected constitutional alcohol isomer is formed, where no migration has taken place.

A pyrrolo-tetrathiafulvalene cage: synthesis and X-ray crystal structure.

[reaction: see text] A novel type of tetrathiafulvalene-cage 4 containing three monopyrrolo-tetrathiafulvalene units has been prepared employing a general and efficient synthetic approach. X-ray crystal structure analysis revealed that the cage is able to accommodate solvent molecules within a cavity in the solid state.

Coupling of metal-based light-harvesting antennas and electron-donor subunits: trinuclear ruthenium(II) complexes containing tetrathiafulvalene-substituted polypyridine ligands.

Three new tetrathiafulvalene-substituted 2,2'-bipyridine ligands, cis-bpy-TTF(1), trans-bpy-TTF(1), and cis-bpy-TTF(2) have been prepared and characterized. X-ray analysis of trans-bpy-TTF(1) is also reported. Such ligands have been used to prepare two new trinuclear Ru(II) complexes, namely, [[(bpy)(2)Ru(micro-2,3-dpp)](2)Ru(bpy-TTF(1))](PF(6))(6) (9; bpy=2,2'-bipyridine; 2,3-dpp=2,3-bis(2'-pyridyl)pyrazine) and [[(bpy)(2)Ru(micro-2,3-dpp)](2)Ru(bpy-TTF(2))](PF(6))(6) (10).

A pyrrolo-tetrathiafulvalene belt and its TCNQ complex: syntheses and X-ray crystal structures.

A general and efficient four-step synthesis of a tetrathiafulvalene-belt 6, starting from the monopyrrolo-tetrathiafulvalene building block 1, is described, together with its 7,7,8,8-tetracyano-p-quinodimethane charge transfer complex. The complexation of the electron acceptor 7,7,8,8-tetracyano-p-quinodimethane by the tetrathiafulvalene-belt 6 was investigated both in solution and in the solid state. [reaction: see text]

A Pyrazole to Furan Rearrangement. Thermolysis of 5-Azido-4-formylpyrazoles.

5-Azido-3-benzyl-4-formyl-1-phenylpyrazoles 1a-c extrude dinitrogen upon heating in toluene to give the corresponding nitrenes, which immediately rearrange via a new ring-opening ring-closure reaction to produce an equimolar mixture of 4-cyano-2-phenyl-3-phenylazofurans 2a-c and 3-benzyl-4-cyano-1-phenylpyrazoles 3a-c. The formation of the 4-cyano-2-phenyl-3-phenylazofurans 2a-c is the first example in the pyrazole series of a nitrene rearrangement, in which the parent heterocyclic system of the product differs from that of the starting material. The isolation of equimolar amounts of the two products points to the fact that their formation occurs by two mechanistically interconnected pathways, between which the exchange of a redox equivalent takes place.

Tetrathiafulvalene Belts with Large Cavities.

The latest member of the cyclophane family, the macrotricyclic tetrathiafulvalene (TTF) "belt", is now available. A general synthetic strategy for the construction of tetraconnected belt-type TTFs (shown schematically) has been developed, made possible by the use of a TTF with two different protecting groups. In the solid-state structure of one of the three TTF-belts prepared two chloroform molecules reside inside the spacious cavity.