Syntheses and photophysical properties of some 5(2)-aryl-2(5)-(4-pyridyl)oxazoles and related oxadiazoles and furans

A number of 5-aryl-2-(4-pyridyl)oxazoles, a 2-aryl-5-(4-pyridyl)oxazole, the related oxadiazole and furan, several 2-(4-pyridyl)cycloalkano[d]oxazoles, and many of their quaternary salts were prepared. No single standard synthesis was effective for preparation of more than a few of the 25 free bases described; methods often unique to a base were employed. Minor variations in structure sometimes produced large differences in absorption and emission wavelengths, as well as in the magnitude of the extinction coefficient. The salts are of interest as laser dyes, scintillation fluors, biological stains, and shifters for luminescent solar concentrators.     

Disulfides of manganese carbonyl. Synthesis of Mn(2)(CO)(7)(mu-S2) and its reactions with tertiary phosphines and arsines

The reaction of Mn(2)(CO)(9)(NCMe) with thiirane yielded the sulfidomanganese carbonyl compounds Mn(2)(CO)(7)(mu-S(2)), 2, Mn(4)(CO)(15)(mu(3)-S(2))(mu(4)-S(2)), 3, and Mn(4)(CO)(14)(NCMe)(mu(3)-S(2))(mu(4)-S(2)), 4, by transfer of sulfur from the thiirane to the manganese complex. Compound 3 was obtained in better yield from the reaction of 2 with CO, and compound 4 is obtained from the reaction of 2 with NCMe. The reaction of 2 with PMe(2)Ph yielded the tetramanganese disulfide Mn(4)(CO)(15)(PMe(2)Ph)(2)(mu(3)-S)(2), 5, and S=PMe(2)Ph. The reaction of 5 with PMe(2)Ph yielded Mn(4)(CO)(14)(PMe(2)Ph)(3)(mu(3)-S)(2), 6, by ligand substitution. The reaction of 2 with AsMe(2)Ph yielded the new complexes Mn(4)(CO)(14)(AsMe(2)Ph)(2)(mu(3)-S(2))(2), 7, Mn(4)(CO)(14)(AsMe(2)Ph)(mu(3)-S(2))(mu(4)-S(2)), 8, Mn(6)(CO)(20)(AsMe(2)Ph)(2)(mu(4)-S(2))(3), 9, and Mn(2)(CO)(6)(AsMe(2)Ph)(mu-S(2)), 10. Reaction of 2 with AsPh(3) yielded the monosubstitution derivative Mn(2)(CO)(6)(AsPh(3))(mu-S(2)), 11. Reaction of 7 with PMe(2)Ph yielded Mn(4)(CO)(15)(AsMe(2)Ph)(2)(mu(3)-S)(2), 12. The phosphine analogue of 7, Mn(4)(CO)(14)(PMe(2)Ph)(2)(mu(3)-S(2))(2), 13, was prepared from the reaction of Mn(2)(CO)(9)(PMe(2)Ph) with Me(3)NO and thiirane. Compounds 2-9 and 11-13 were characterized by single-crystal X-ray diffraction. Compound 2 contains a disulfido ligand that bridges two Mn(CO)(3) groups that are joined by a Mn-Mn single bond, 2.6745(5) A in length. A carbonyl ligand bridges the Mn-Mn bond. Compounds 3 and 4 contain four manganese atoms with one triply bridging and one quadruply bridging disulfido ligand. Compounds 5 and 6 contain four manganese atoms with two triply bridging sulfido ligands. Compound 9 contains three quadruply bridging disulfido ligands imbedded in a cluster of six manganese atoms.     

Barrier-free intermolecular proton transfer induced by excess electron attachment to the complex of alanine with uracil

The photoelectron spectrum of the uracil-alanine anionic complex (UA)(-) has been recorded with 2.540 eV photons. This spectrum reveals a broad feature with a maximum between 1.6 and 2.1 eV. The vertical electron detachment energy is too large to be attributed to an (UA)(-) anionic complex in which an intact uracil anion is solvated by alanine, or vice versa. The neutral and anionic complexes of uracil and alanine were studied at the B3LYP and second-order M?ller-Plesset level of theory with 6-31++G(*) (*) basis sets. The neutral complexes form cyclic hydrogen bonds and the three most stable neutral complexes are bound by 0.72, 0.61, and 0.57 eV. The electron hole in complexes of uracil with alanine is localized on uracil, but the formation of a complex with alanine strongly modulates the vertical ionization energy of uracil. The theoretical results indicate that the excess electron in (UA)(-) occupies a pi(*) orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of alanine to the O8 atom of uracil. As a result, the four most stable structures of the uracil-alanine anionic complex can be characterized as a neutral radical of hydrogenated uracil solvated by a deprotonated alanine. Our current results for the anionic complex of uracil with alanine are similar to our previous results for the anion of uracil with glycine, and together they indicate that the BFPT process is not very sensitive to the nature of the amino acid's hydrophobic residual group. The BFPT to the O8 atom of uracil may be relevant to the damage suffered by nucleic acid bases due to exposure to low energy electrons.     

PHOTOCHEMICAL STUDIES ON THE ANTIINFLAMMATORY DRUG DICLOFENAC

Irradiation with UVA light of the anti-inflammatory drug diclofenac [2-(2,6-dichloroanilino)phenylacetic acid] in aqueous buffer or methanol solution leads to sequential loss of both chlorine substituents and ring closure to carbazole-1-acetic acid as the major product. Minor products result from substitution by the solvent. The photosensitizing properties of diclofenac and its major photoproduct were tested with singlet oxygen substrates and in the free radical polymerization of acrylamide. Although the major carbazole product is a weakly phototoxic agent, able to generate singlet oxygen more efficiently than diclofenac, the free radical photodechlorination process is postulated as the probable initiation step of in vivo photosensitivity responses.     

Thermal analytical investigation of ancient mortars from gothic churches

The use of thermal analysis in studying ancient mortars in English cathedrals is explained. Thermal analysis can be used to investigate both mortar and stone in dated structures. Analysis of ancient mortars show that though recarbonated, they remain soft, yielding to structural deformations. The use of hard (cement mortar) in modern renovation can result in micro-cracking in the stone and subsequent chemical attack from the atmosphere. Contrary to the literature, data developed in the present study suggests that most medieval mortars have reached a near total state of recarbonation.     

Further studies of the reactions of PtRu5(μ6-C)(CO)16 with alkynes: The preparation and structural characterizations of PtRu5(CO)13(μ-EtC2Et)(μ3-EtC2Et)(μ5-C) and Pt2Ru6(CO)17(μ-η5-Et4C5)(μ3-EtC2Et) (μ6-C)

The reaction of PtRu₅(CO)₁₆(μ₆-C),1 with 3-hexyne in the presence of UV irradiation produced two new electron-rich platinum-ruthenium cluster complexes PtRu₅(CO)₁₃(μ-EtC₂Et)(μ₃-EtC₂Et)(μ₅-C),2 (20% yield) and Pt₂Ru₆(CO)₁₇(μ-η⁵-Et₄C₅)(μ₃-EtC₂Et) (μ₆-C),3 (7% yield). Both compounds were characterized by single-crystal X-ray diffraction analyses. Compound2 contains of a platinum capped square pyramidal cluster of five ruthenium atoms with the carbido ligand located in the center of the square pyramid. A EtC₂Et ligand bridges one of the PtRu₂ triangles and the Ru-Pt bond between the apical ruthenium atom and the platinum cap. The structure of compound3 consists of an octahedral PtRu₅ cluster with an interstitial carbido ligand and a platinum atom capping one of the PtRu₂ triangles. There is an additional Ru(CO)₂ group extending from the platinum atom in the PtRu₅ cluster that contains a metallated tetraethylcyclopentadienyl ligand that bridges to the platinum capping group. There is also a EtC₂Et ligand bridging one of the PtRu₂ triangular faces to the capping platinum atom. Compounds2 and3 both contain two valence electrons more than the number predicted by conventional electron counting theories, and both also possess unusually long metal-metal bonds that may be related to these anomalous electron configurations. Crystal data for2, space group Pna2₁,a=19.951(3) Å,b=9.905(2) Å,c=17.180(2) Å,Z=2, 1844 reflections,R=0.036; for3, space group Pna2₁,α=13.339(1) Å,b=14.671(2) Å,c=11.748(2) Å, α=100.18(1)°, β=95.79(1)°, γ=83.671(9)°,Z=2, 3127 reflections,R=0.026.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

New rhenium-tin cluster adds palladium phosphine groups across Re-Sn bonds

The new rhenium-tin complex Re2(CO)8(mu-SnPh2)2, 1 was obtained in 52% yield from the reaction of Re2(CO)8(mu-H)[mu-C(H)C(H)Bu] with Ph3SnH. Compound 1 contains two SnPh2 groups bridging a long Re-Re single bond, Re-Re = 3.1971(4) A [3.1902(4) A], Re-Sn = 2.7429(4) A [2.7445(4) A], and 2.7675(4) [2.7682(5) A]. A bis-Pd(PBut3) adduct of 1, Pd2Re2(CO)8(mu-SnPh2)2(PBut3)2, 2 was obtained from the reaction of 1 with Pd(PBut3)2. Compound 2 contains Pd(PBut3) groups bridging two of its four Re-Sn bonds. The Re-Re bond and the unbridged Re-Sn bonds in 2 are significantly longer than those in 1, 3.245(1) A and 2.8167(14) A, respectively. Fenske-Hall molecular orbital calculations on 1 and 2 have been performed to explain the metal-metal bonding in these unusual mixed-metal polynuclear metal complexes.     

Simultaneous determination of selenium and antimony compounds by capillary electrophoresis with indirect fluorescence detection

Capillary electrophoresis (CE) with indirect fluorescence detection was used to analyze selenium (selenite, selenate, selenomethionine, and selenocystine) and antimony (antimonite and antimonate) compounds. The separation was achieved by CE in 6 min with a 1.2 mM fluorescein solution at pH 9.5. Fluorescein also functioned as a background fluorophore for the indirect detection of these nonfluorescent species. Linearity of more than two orders of magnitude was generally obtained. Precision of migration times and peak areas was less than 1.0% and 7.2%, respectively. The concentration limits of detection (CLODs) was in the microM range. The detection sensitivity was generally dependent upon the transfer ratio (TR, defined as the number of moles of fluorescein ions displaced by one mole of analyte ions) of each species.     

Ruthenium Carbonyl Cluster Complexes with Phenylgermyl Ligands from the Reactions of Ph<Subscript>3</Subscript>GeH with Ru(CO)<Subscript>5</Subscript> and Ru<Subscript>3</Subscript>(CO)<Subscript>12</Subscript>

Four new triphenylgermylruthenium carbonyl compounds HRu(CO)₄GePh₃, 14; Ru(CO)₄(GePh₃)₂, 15; Ru₂(CO)₈(GePh₃)₂, 16; and Ru₃(CO)₉(GePh₃)₃(μ-H)₃, 17 were obtained from the reaction of Ru(CO)₅ with Ph₃GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)₅ and an oxidative addition of the GeH bond of the Ph₃GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh₃ ligands in the six coordinate complex. Compound 16 contains two Ru(CO)₄(GePh₃) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh₃ ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru₃(CO)₁₀(μ-GePh₂)₂, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh₂ ligands bridging two different edges of the cluster and one bridging CO ligand. Ru₃(CO)₁₂ was found to react with Ph₃GeH at 97 °C to yield three products: 15, and two new compounds Ru₃(CO)₉(μ-GePh₂)₃, 19 and Ru₂(CO)₆(μ-GePh₂)₂(GePh₃)₂, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh₂ ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh₂ ligands and a terminal GePh₃ ligand on each metal atom. All compounds were characterized by a combination of IR, ¹H NMR, single-crystal X-ray diffraction analyses. This report is dedicated to Professor Dieter Fenske on the occasion of his 65th birthday for his many pioneering contributions to the chemistry of metal chalcogenide cluster complexes.