Synthesis,extended Hückel molecular orbital calculations,and X-ray diffraction structure of the pentamethylcyclopentadienylruthenium complex Cp*Ru(NO)(2,3-quinoxalinediolate)

The reaction between Cp^*Ru(NO)Cl₂ and the heterocyclic compound 2,3-quinoxalinediol in the presence of methanolic KOH leads to the formation of the new piano-stool compound Cp^*Ru(NO)(2,3-quinoxalinediolate) (1). Product isolation and characterization by solution spectroscopic methods (¹H and¹³C NMR and IR) are described. The solid-state structure of Cp^*Ru(NO)(2,3-quinoxalinediolate) confirms the replacement of each chloride ligand in Cp^*Ru(NO)Cl₂ by an oxygen group of the 2,3-quinoxalinediol ligand. Cp^*Ru(NO)(2,3-quinoxalinediolate) crystallizes in the orthorhombic space group Pbca, a=14.846(1) Å,b=12.718(1) Å,c=18.255(2) Å,V=3446.7(5) ų,Z=8,d _calc=1.643 g·cm^–3;R=0.0364,R _w=0.0393 for 1245 observed reflections withI>3(I). The observed Ru–N–O bond angle of 156.3(7)° in the X-ray structure of1 confirms the nonlinear nature of the nitrosyl linkage. This bend in the nitrosyl moiety away from the quinoxalinediolate ligand presumably results from solid-state packing forces and does not derive from electronic interactions, on the basis of extended Hückel molecular orbital calculations. The MO properties of1 are compared with other Cp^*Ru(NO)-substituted complexes previously synthesized in these laboratories.     

Solution interactions and solid-matrix interactions in beta-cyclodextrin solid-matrix luminescence

A variety of liquid chromatographic, solution fluorescence, and extraction data were obtained in an attempt to correlate solution interactions with solid-matrix interactions for solute-beta-cyclodextrin complexes. From the chromatographic data, dissociation constants were calculated for the complexes. Fluorescence spectral characteristics were obtained for sodium chloride, glucose, and beta-cyclodextrin solutions of several solutes. In addition, extraction experiments were performed in an attempt to remove the solutes from the beta-cyclodextrin solid matrix. Generally, the results revealed that there were no simple correlations between the solution data and solid-matrix luminescence data. However, the extraction results yielded important information related to the solute interactions in the solid matrix.     

Dual Brønsted acid/nucleophilic activation of carbonylimidazole derivatives

Carbonylimidazole derivatives have been found to be highly active acylation reagents for esterification and amidation in the presence of pyridinium salts. These reactions are thought to involve both Br?nsted acid and nucleophilic catalysis. This mode of activation has been applied to the synthesis of difficult to access oxazolidinones, as well as esters and amides. Finally, the use of pyridinium salts has been shown to accelerate the esterification of carboxylic acids with imidazole carbamates.     

PHOTOREACTIVITY OF 5-GERANOXYPSORALEN AND LACK OF PHOTOREACTION WITH DNA

5-Geranoxypsoralen, commonly called bergamottin, a major furocoumarin contained in bergamot oil, is reported in vitro as a highly photoreactive psoralen. In ethanol, it exhibits quite a high triplet state quantum yield (approximately 0.37). The triplet state is involved in subsequent photochemistry which depends on the initial concentration and on the presence of oxygen. In contrast to most psoralens, absorption and fluorescence data suggest that 5-geranoxypsoralen does not interact with DNA in the dark. No UVA-induced interstrand cross-links in DNA were shown.     

Electronic effects in the pt-catalyzed cycloisomerization of propargylic esters: synthesis of 2,3-disubstituted indolizines as a mechanistic probe

The initial 5-exo versus 6-endo cyclization of the acyl group onto the activated alkyne of propargylic esters has been found to be dependent on electronic effects of the acyl, alkyne, and propargylic carbon substituents. These electronic effects control the ratio of 2,3-disubstituted versus 1,3-disubstituted indolizine products formed when substrates bearing pyridines at the alkyne terminus are used.     

Pincer ligand coordination at a triosmium cluster: X-ray structures of 1,2-Os3(CO)10[4,6-bis(diphenylphosphinomethyl)-m-xylene] and 1,2-Os3(CO)10[1-diphenylphosphino-1-{(2,4-dimethyl-5-diphenylphosphinomethyl)phenyl}-propan-2-ol]

The reaction between the triosmium cluster 1,2-Os₃(CO)₁₀(MeCN)₂ and the diphosphine pincer ligand 4,6-bis(diphenylphosphinomethyl)-m-xylene (dppx) has been examined and found to yield the pincer-bridged cluster 1,2-Os₃(CO)₁₀(dppx) (2) as the major product, in addition to the pincer-bridged cluster 1,2-Os₃(CO)₁₀[1-diphenylphosphino-1-{(2,4-dimethyl-5-diphenylphosphinomethyl)phenyl}-propan-2-ol] (3) in trace amounts (<2% yield). Both cluster products have been isolated and their molecular structures determined by crystallographic analyses. The structural highlights of compounds 2 and 3, which represent the first examples of pincer-ligated metal clusters, are discussed. The origin of the functionalized diphosphine ligand in 3 is traced to the ethanol solvent that was used in the recrystallization of the dppx ligand.     

Ru–bis(pyridine)pyrazolate (bpp)‐Based Water‐Oxidation Catalysts Anchored on TiO2: The Importance of the Nature and Position of the Anchoring Group

Three distinct functionalisation strategies have been applied to the in,in‐[{Ru^II(trpy)}₂(μ‐bpp)(H₂O)₂]³⁺ (trpy=2,2′:6′,2′′‐terpyridine, bpp=bis(pyridine)pyrazolate) water‐oxidation catalyst framework to form new derivatives that can adsorb onto titania substrates. Modifications included the addition of sulfonate, carboxylate, and phosphonate anchoring groups to the terpyridine and bis(pyridyl)pyrazolate ligands. The complexes were characterised in solution by using 1D NMR, 2D NMR, and UV/Vis spectroscopic analysis and electrochemical techniques. The complexes were then anchored on TiO₂‐coated fluorinated tin oxide (FTO) films, and the reactivity of these new materials as water‐oxidation catalysts was tested electrochemically through controlled‐potential electrolysis (CPE) with oxygen evolution detected by headspace analysis with a Clark electrode. The results obtained highlight the importance of the catalyst orientation with respect to the titania surface in regard to its capacity to catalytically oxidize water to dioxygen.     

Application of a Palladium‐Catalyzed C−H Functionalization/Indolization Method to Syntheses of cis‐Trikentrin A and Herbindole B

We describe herein formal syntheses of the indole alkaloids cis‐trikentrin A and herbindole B from a common meso‐hydroquinone intermediate prepared by a ruthenium‐catalyzed [2+2+1+1] cycloaddition that has not been used previously in natural product synthesis. Key steps include a sterically demanding Buchwald–Hartwig amination as well as a unique C(sp³)?H amination/indole formation. Studies toward a selective desymmetrization of the meso‐hydroquinone are also reported.     

Stable Tetrabenzo-Chichibabin's Hydrocarbons: Tunable Ground State and Unusual Transition between Their Closed-Shell and Open-Shell Resonance Forms

Stable open-shell polycyclic aromatic hydrocarbons (PAHs) are of fundamental interest due to their unique electronic, optical, and magnetic properties and promising applications in materials sciences. Chichibabin's hydrocarbon as a classical open-shell PAH has been investigated for a long time. However, most of the studies are complicated by their inherent high reactivity. In this work, two new stable benzannulated Chichibabin's hydrocarbons 1-CS and 2-OS were prepared, and their electronic structure and geometry in the ground state were studied by various experiments (steady-state and transient absorption spectra, NMR, electron spin resonance (ESR), superconducting quantum interference device (SQUID), FT Raman, X-ray crystallographic etc.) and density function theory (DFT) calculations. 1-CS and 2-OS exhibited tunable ground states, with a closed-shell quinoidal structure for 1-CS and an open-shell biradical form for 2-OS. Their corresponding excited-state forms 1-OS and 2-CS were also chemically approached and showed different decay processes. The biradical 1-OS displayed an unusually slow decay to the ground state (1-CS) due to a large energy barrier (95 ± 2.5 kJ/mol) arising from severe steric hindrance during the transition from an orthogonal biradical form to a butterfly-like quinoidal form. The quick transition from the quinoidal 2-CS (excited state) to the orthogonal biradicaloid 2-OS (ground state) happened during the attempted synthesis of 2-CS. Compounds 1-CS and 2-OS can be oxidized into stable dications by FeCl(3) and/or concentrated H(2)SO(4). The open-shell 2-OS also exhibited a large two-photon absorption (TPA) cross section (760 GM at 1200 nm).     

0–1 laws for maps

A class of finite structures has a 0–1 law with respect to a logic if every property expressible in the logic has a probability approaching a limit of 0 or 1 as the structure size grows. To formulate 0–1 laws for maps (i.e., embeddings of graphs in a surface), it is necessary to represent maps as logical structures. Three such representations are given, the most general being the full cross representation based on Tutte's theory of combinatorial maps. The main result says that if a class of maps has two properties, richness and large representativity, then the corresponding class of full cross representations has a 0–1 law with respect to first‐order logic. As a corollary the following classes of maps on a surface of fixed type have a first‐order 0–1 law: all maps, smooth maps, 2‐connected maps, 3‐connected maps, triangular maps, 2‐connected triangular maps, and 3‐connected triangular maps. ©1999 John Wiley & Sons, Inc. Random Struct. Alg., 14, 215–237, 1999