Ruthenium Cluster Chemistry with Ph2PC6H4-4-C≡CH

The new phosphines Ph₂PC₆H₄-4-CCR [R=SiMe₃ (1), H (2)] have been used to prepare Ru₃(CO)₉(Ph₂PC₆H₄-4-CCSiMe₃)₃ (4) and Ru(CCC₆H₄-4-PPh₂)(PPh₃)₂(-C₅H₅) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru₃(CO)₉(Ph₂PC₆H₄-4-CCH)₃ (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh₃)₂(-C₅H₅)]PF₆ or reaction of Ru₃(CO)₁₂ with 3 gives Ru₃(CO)₉{(Ph₂PC₆H₄-4-CC)Ru(PPh₃)₂(-C₅H₅)}₃ (6). Complexes 3–6 have been studied by cyclic voltammetry. Proceeding from Ru₃(CO)₁₂ to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C₆H₁₄: space group P¯1, a=12.760(1) Å, b=17.077(1) Å, c=17.924(2) Å, =108.656(5)°, =96.344(5)°, =93.523(5)°, V=3658.4(6) ų, Z=2, R=0.078, R_w=0.105 for 5008 reflections [I>2.00(I)].     

Autoxidation of cyclohexane: conventional views challenged by theory and experiment.

In spite of its industrial importance, the detailed reaction mechanism of cyclohexane autoxidation by O2 is still insufficiently known. Based on quantum chemical potential energy surfaces, rate coefficients of the primary and secondary chain propagation steps involving the cyclohexylperoxyl (CyOO) radical were evaluated using multiconformer transition-state theory. Including tunneling and hindered-internal-rotation effects, the rate coefficient for hydrogen-atom abstraction from cyclohexane (CyH) by CyOO was calculated to be k(T)= 1.46 x 10(-11) x exp(-17.8 kcal mol(-1)/ RT) cm3s(-1) (300-600K), close to the experimental data. A "Franck-Rabinowitch cage" reaction between the nascent cyclohexylhydroperoxide (CyOOH) and cyclohexyl radical, products from CyOO + CyH, is put forward as an initially important cyclohexanol (CyOH) formation channel. alphaH abstraction by CyOO. from cyclohexanone was calculated to be only about five times faster than that from CyH, too slow to explain all the observed side products. The a-hydrogen (alphaH) abstractions from CyOH and CyOOH by CyOO. are predicted to be about 10 and 40 times faster, respectively, than the CyOO. +CyH reaction. The very fast CyOO.+CyOOH reaction proceeds through the unstable Cy-alphaH .OOH radical that decomposes spontaneously into the ketone (Q=O) plus the OH radical; the "hot" .OH is found to produce the bulk of the alcohol via a second, "activated cage" reaction analogous to that above. It is thus shown how the very reactive CyOOH intermediate is the predominant source of ketone and alcohol, while it also leads to some side products. The alpha-hydroxycyclohexylperoxyl radical formed during the moderately fast oxidation of CyOH is shown to decompose fast into HO2 + cyclohexanone in a rapidly equilibrated reaction, which constitutes a smaller, second ketone source. These two fast cyclohexanone forming routes avoid the need for unfavorable molecular routes hitherto invoked as ketone sources. The theoretical predictions are supported and complemented by experimental findings. The newly proposed scheme is also largely applicable to the oxidation of other hydrocarbons, such as toluene, xylene, and ethylbenzene.     

Solid-phase synthesis of quinoxaline, thiazine, and oxazine analogs through a benzyne intermediate

A solid-phase synthetic route to quinoxaline, thiazine, and oxazine analogs is described. N-Alloc-3-amino-3-(2,4-difluoro-5-nitrophenyl)propanoic acid was tethered to Rink resin via its carboxylic acid group. The 4-arylfluorine was displaced with a primary amine, alcohol, or thiol to create, respectively, a resin bound aniline, phenol, or thiophenol derivative with one diversity element and one single atom (e.g., N, S, or O) diversity point. A fused heterocyclic system was subsequently created via a benzyne heterocyclization initiated by dehydrofluorination with strong base. Acid treatment released the desired products in high yield and moderate purity.     

Semiclassical approach to collision-induced emission in the presence of intense laser radiation: An aspect in the study of cooperative chemical and optical pumping

Collion-induced emission in molecular systems in an intense laser field is studied using the semiclassical approach, with a view towards cooperative chemical and optical pumping in laser production. The formalism is developed with the electronic-field representation, which treats collision and radiative interaction on the same footing. Electronic-field surfaces can be regarded as forming spectra for spontaneous emission; and particular emission events can be accounted for by propagating classical trajectories on emission electronic-field surfaces. Pre-emission loss from the excited state is dealt with by propagating classical trajectories on a loss surface along a complex contour of emission branch points. This loss surface is derived on the basis of localized radiative couplings between electronic-field states and provides a framework to treat the general problem of discrete state-continuum interactions. The formalism is applied to a two-state, collinear exponential model to compute S-matrix elements and transition probabilities between asymptotic states.     

A trinuclear heterobimetallic Ru(II)/Pt(II) complex as a chemodosimeter selective for sulfhydryl-containing amino acids and peptides

A trinuclear heterobimetallic Ru(II)/Pt(II) complex, cis-{Ru(phen)2[CN-Pt(DMSO)Cl2]2} (phen = 1,10-phenanthroline), is able to function as a "switch-on" luminescent chemodosimeter for sulfhydryl-containing amino acids and peptides via specific binding of the amino acids/peptides with the Pt(II) centers and the subsequent cleavage of the Ru(II)-Pt(II) cyano-bridge.     

Bis(m-phenylene)-32-crown-10-based cryptands, powerful hosts for paraquat derivatives

Four new bis(m-phenylene)-32-crown-10-based cryptands with different third bridges were prepared. Their complexes with paraquat derivatives were studied by proton NMR spectroscopy, mass spectrometry, and X-ray analysis. It was found that these cryptands bind paraquat derivatives very strongly. Specifically, a diester cryptand with a pyridyl nitrogen atom located at a site occupied by either water or a PF(6) anion in analogous complexes exhibited the highest association constant K(a) = 5.0 x 10(6) M(-1) in acetone with paraquat, 9000 times greater than the crown ether system. X-ray structures of this and analogous complexes demonstrate that improved complexation with this host is a consequence of preorganization, adequate ring size for occupation by the guest, and the proper location of the pyridyl N-atom for binding to the beta-pyridinium hydrogens of the paraquat guests. This readily accessible cryptand is one of the most powerful hosts reported for paraquats.     

A class of general systems of KdV type I

We consider some wide class of general systems of Korteweg-de Vries equations which contain nonlinear terms with derivatives of higher order, we have proved the existence of generalized solution for this system and the asymptotic behavior ast and blow up property of the solution are discussed.     

Titanium alkoxide complexes: condensed phase and gas phase comparisons

The complex [Ti(2,4-dimethyl-2,4-pentanediolate)2]2 (1) has been synthesized from [Ti(OiPr)4] by transesterification with a stoichiometric amount of 2,4-dimethyl-2,4-pentanediol. We have characterized complex 1 in the solid state by single-crystal X-ray diffraction and in the gas phase by desorption chemical ionization mass spectrometry (DCI-MS). The structural and mass spectrometric data show complex 1 to be stable as a dimer in both the solid and gas phases. The retention of dimeric nuclearity in the gas phase sets complex 1 apart from other simple titanium alkoxide complexes [Ti(OiPr)4] and [Ti(OMe)4]4 that give rise to respective families of molecular ions in the DCI-MS experiment. The highest mass molecular ions for Ti alkoxide complexes in the gas phase may reveal the highest nuclearity that these complexes achieve in condensed phases. According to this interpretation the complex [Ti(OiPr)4] is principally dimeric in the gas phase and probably also in the pure liquid phase and should be represented by the formula [Ti(OiPr)4]2.     

Chemistry of condensed thiophenes. IV. Acetylation of phenanthro[4,5-bcd]thiophene

Treatment of phenanthro[4,5-bcd]thiophene ( 2 ) with acetyl chloride and aluminum chloride in nitrobenzene gives acetylation of positions ortho and para to the heteroatomic sulfur atom. In separate experiments, mixtures of 1- and 3-acetyl (50% yield, ratio 1.9:1) or of 1,5-, 1,7-, and 3,5-diacetyl (79% yield, ratio 3:1:1) derivatives were obtained. Isolated as isomerically pure products were the 1-acetyl and the 1,5-diacetyl compounds, as well as the oximes of the 1- and 3-acetyl derivatives. Comparison of these results is made with those reported for nitration of 2 , which also occurs ortho and para to the sulfur atom, and with nitration and acetylation of pyrene (the benzolog of 2 ) which substitutes in the corresponding positions.     

Ligand-assisted reduction of osmium tetroxide with molecular hydrogen via a [3+2] mechanism

Osmium tetroxide is reduced by molecular hydrogen in the presence of ligands in both polar and nonpolar solvents. In CHCl3 containing pyridine (py) or 1,10-phenanthroline (phen), OsO4 is reduced by H2 to the known Os(VI) dimers L2Os(O)2(mu-O)2Os(O)2L2 (L2 = py2, phen). However, in the absence of ligands in CHCl3 and other nonpolar solvents, OsO4 is unreactive toward H2 over a week at ambient temperatures. In basic aqueous media, H2 reduces OsO4(OH)n(n-) (n = 0, 1, 2) to the isolable Os(VI) complex, OsO2(OH)4(2-), at rates close to that found in py/CHCl3. Depending on the pH, the aqueous reactions are exergonic by deltaG = -20 to -27 kcal mol(-1), based on electrochemical data. The second-order rate constants for the aqueous reactions are larger as the number of coordinated hydroxide ligands increases, k(OsO4) = 1.6(2) x 10(-2) M(-1) s(-1) < k(OsO4(OH)-) = 3.8(4) x 10(-2) M(-1) s(-1) < k(OsO4(OH)2(2-)) = 3.8(4) x 10(-1) M(-1) s(-1). The observation of primary deuterium kinetic isotope effects, k(H2)/k(D2) = 3.1(3) for OsO4 and 3.6(4) for OsO4(OH)-, indicates that the rate-determining step in each case involves H-H bond cleavage. Density functional calculations and thermochemical arguments favor a concerted [3+2] addition of H2 across two oxo groups of OsO4(L)n and argue against H* or H- abstraction from H2 or [2+2] addition of H2 across one Os=O bond. The [3+2] mechanism is analogous to that of alkene addition to OsO4(L)n to form diolates, for which acceleration by added ligands has been extensively documented. The observation that ligands also accelerate H2 addition to OsO4(L)n highlights the analogy between these two reactions.