Electron and oxygen transfer in polyoxometalate, H(5)PV(2)Mo(10)O(40), catalyzed oxidation of aromatic and alkyl aromatic compounds: evidence for aerobic Mars-van Krevelen-type reactions in the liquid homogeneous phase

The mechanism of aerobic oxidation of aromatic and alkyl aromatic compounds using anthracene and xanthene, respectively, as a model compound was investigated using a phosphovanadomolybdate polyoxometalate, H(5)PV(2)Mo(10)O(40), as catalyst under mild, liquid-phase conditions. The polyoxometalate is a soluble analogue of insoluble mixed-metal oxides often used for high-temperature gas-phase heterogeneous oxidation which proceed by a Mars-van Krevelen mechanism. The general purpose of the present investigation was to prove that a Mars-van Krevelen mechanism is possible also in liquid-phase, homogeneous oxidation reactions. First, the oxygen transfer from H(5)PV(2)Mo(10)O(40) to the hydrocarbons was studied using various techniques to show that commonly observed liquid-phase oxidation mechanisms, autoxidation, and oxidative nucleophilic substitution were not occurring in this case. Techniques used included (a) use of (18)O-labeled molecular oxygen, polyoxometalate, and water; (b) carrying out reactions under anaerobic conditions; (c) performing the reaction with an alternative nucleophile (acetate) or under anhydrous conditions; and (d) determination of the reaction stoichiometry. All of the experiments pointed against autoxidation and oxidative nucleophilic substitution and toward a Mars-van Krevelen mechanism. Second, the mode of activation of the hydrocarbon was determined to be by electron transfer, as opposed to hydrogen atom transfer from the hydrocarbon to the polyoxometalate. Kinetic studies showed that an outer-sphere electron transfer was probable with formation of a donor-acceptor complex. Further studies enabled the isolation and observation of intermediates by ESR and NMR spectroscopy. For anthracene, the immediate result of electron transfer, that is formation of an anthracene radical cation and reduced polyoxometalate, was observed by ESR spectroscopy. The ESR spectrum, together with kinetics experiments, including kinetic isotope experiments and (1)H NMR, support a Mars-van Krevelen mechanism in which the rate-determining step is the oxygen-transfer reaction between the polyoxometalate and the intermediate radical cation. Anthraquinone is the only observable reaction product. For xanthene, the radical cation could not be observed. Instead, the initial radical cation undergoes fast additional proton and electron transfer (or hydrogen atom transfer) to yield a stable benzylic cation observable by (1)H NMR. Again, kinetics experiments support the notion of an oxygen-transfer rate-determining step between the xanthenyl cation and the polyoxometalate, with formation of xanthen-9-one as the only product. Schemes summarizing the proposed reaction mechanisms are presented.     

A phototriggered molecular spring for aerobic catalytic oxidation reactions

The first catalytic oxidation reactions with cofacial bisporphyrins using molecular oxygen as the terminal oxidant are presented. The photocatalytic reactions proceed under mild conditions (ambient temperature and pressure) without the need for a co-reductant. A systematic reactivity study of the photooxidation of dimethyl sulfide (DMS) with a homologous series of bisiron(III) mu-oxo porphyrins containing dibenzofuran, xanthene, or no bridge reveals that the facility of these processes is markedly dependent on the vertical flexibility of the catalyst to provide a phototriggered molecular spring.     

PHOTODYNAMIC INACTIVATION OF SARCOPLASMIC RETICULUM VESICLE MEMBRANES BY XANTHENE DYES

Abstract— Photosensitized oxidation of sarcoplasmic reticulum (SR) vesicle membranes by a series of xanthene dyes was investigated. With increasing dye concentration and illumination time, the calcium ion uptake, ATPase activity and UV fluorescence intensity of SR decreased, and the absorbance at 241 nm increased. In xanthene dyes, the order of inactivation of the calcium uptake and ATPase activity of SR was in accord with decreasing order, of fluorescence intensity and increasing order of absorbance at 241 nm. Some regular relationships exist between the molecular structures of xanthene dyes and the photodynamic inactivation of SR membranes.     

Porphyrin architectures bearing functionalized xanthene spacers

A modular synthetic strategy for the construction of cofacial porphyrin architectures bearing hydrogen-bond synthons on a xanthene platform is presented. The convergent approach is based on a xanthene aldehyde-ester building block that is easily obtainable on a multigram scale with minimal purification. Treatment of this xanthene derivative with a variety of aryl aldehydes and pyrrole under standard Lindsey conditions affords a family of meso-substituted porphyrins bearing a single functionalized xanthene spacer. Direct modification of the hydrogen-bond synthon after macrocyclization proceeds smoothly to furnish porphyrin systems with a variety of cofacial functionalities (e.g., carboxylic acid, ester, amide). Porphyrins bearing two trans-functionalized xanthene spacers are prepared by the MacDonald [2 + 2] condensation of the xanthene aldehyde-ester with readily available 5-aryl-substituted dipyrromethanes such as 5-mesityldipyrromethane to afford the pure alpha,alpha- and alpha,beta-porphyrin atropisomers after chromatographic separation. The versatility of this synthetic method offers intriguing opportunities for the use of these and related templates for the study of proton-coupled activation of small molecules.     

Highly efficient and green synthesis of 14-aryl(alkyl)-14H-dibenzo[a,j]xanthene and 1,8-dioxooctahydroxanthene derivatives catalyzed by reusable zirconyl triflate [ZrO(OTf)2]under solvent-free conditions

An efficient,convenient and green method has been introduced for the preparation of 14-aryl（alkyl）-14H-dibenzo[a,j]xanthene and 1,8-dioxooctahydroxanthene derivatives by the reaction of aldehydes with 2-naphthol and 5,5-dimethyl-1,3-cyclohexanedione, respectively,in the presence of ZrO（OTf）₂ as a reusable catalyst under solvent-free conditions.In addition,very short reaction times, excellent yields,straightforward procedure,and relatively non-toxicity of the catalyst are other noteworthy advantages of the present method.     

Intramolecular formal [4+2] cycloaddition reactions of secondary and tertiary aryldiacetylene alcohols

Thermal and thionyl chloride induced cycloaromatizations of secondary and tertiary aryldiacetylene alcohols were studied. The secondary alcohol did not respond to thionyl chloride, but in all the other cases presumptive biradical intermediates evolved either by intramolecular radical coupling or, when derived from a xanthene scaffold, by intramolecular radical acylation to a diketone that finally afforded a p-methylene-quinone.     

Fluoro-tagged osmium and iridium nanoparticles in oxidation reactions

Osmium and iridium metal nanoparticles were supported on a fluorous organic-inorganic hybrid material prepared by the sol-gel process. Moreover, we also found that the thermolysis of the Ir₄(CO)₁₂ cluster in simply diphenylether also gave Ir(0) nanoparticles. All the materials were studied as catalysts in oxidation processes. Fluoro-tagged iridium nanoparticles were particularly active in aerobic oxidation processes, whereby the catalytic activity could be greatly enhanced through a simple pre-activation procedure. With this material, benzylic alcohols could be oxidized under O₂ balloon in the absence of a basic additive; the oxidative stopped selectively to the corresponding benzaldehyde. Promisingly, the same reaction conditions were used in a benzylic CH oxidation of xanthene.     

Direct photooxidation and xanthene-sensitized oxidation of naphthols: quantum yields and mechanism

The photoinduced oxidation of 1-naphthol to 1,4-naphthoquinone and of 5-hydroxy-1-naphthol to 5-hydroxy-1,4-naphthoquinone was studied by steady-state and time-resolved techniques. The direct photooxidation of naphthols in methanol or water takes place by reaction of the naphoxyl radical ((?)ONaph) with the superoxide ion radical (O(2)(?-)), the latter of which results from the reaction of the solvated electron with oxygen after photoionization. The sensitized oxidation takes place by energy transfer from the xanthene triplet state to oxygen. From the two oxygen atoms, which are consumed, one is incorporated into the naphthol molecule giving naphthoquinone and the second gives rise to water. The effects of eosin, erythrosin, and rose bengal in aqueous solution, pH, and the oxygen and naphthol concentrations were studied. The quantum yield of the photosensitized transformation was determined, which increases with the naphthol concentration and is largest at pH > 10. The quantum yield of oxygen uptake is similar. The pathway involving singlet molecular oxygen is suggested to operate for the three sensitizers. The alternative pathway via electron transfer from the naphthol to the xanthene triplet state and subsequent reaction of (?)ONaph with O(2)(?-), the latter of which is formed by scavenging of the xanthene radical anion by oxygen, does also contribute.     

Hydrogen‐Atom Abstraction Reactions by Manganese(V)– and Manganese(IV)–Oxo Porphyrin Complexes in Aqueous Solution

High‐valent manganese(IV or V)–oxo porphyrins are considered as reactive intermediates in the oxidation of organic substrates by manganese porphyrin catalysts. We have generated Mn^V– and Mn^IV–oxo porphyrins in basic aqueous solution and investigated their reactivities in C? H bond activation of hydrocarbons. We now report that Mn^V– and Mn^IV–oxo porphyrins are capable of activating C? H bonds of alkylaromatics, with the reactivity order of Mn^V–oxo>Mn^IV–oxo; the reactivity of a Mn^V–oxo complex is 150 times greater than that of a Mn^IV–oxo complex in the oxidation of xanthene. The C? H bond activation of alkylaromatics by the Mn^V– and Mn^IV–oxo porphyrins is proposed to occur through a hydrogen‐atom abstraction, based on the observations of a good linear correlation between the reaction rates and the C? H bond dissociation energy (BDE) of substrates and high kinetic isotope effect (KIE) values in the oxidation of xanthene and dihydroanthracene (DHA). We have demonstrated that the disproportionation of Mn^IV–oxo porphyrins to Mn^V–oxo and Mn^III porphyrins is not a feasible pathway in basic aqueous solution and that Mn^IV–oxo porphyrins are able to abstract hydrogen atoms from alkylaromatics. The C? H bond activation of alkylaromatics by Mn^V– and Mn^IV–oxo species proceeds through a one‐electron process, in which a Mn^IV–‐oxo porphyrin is formed as a product in the C? H bond activation by a Mn^V–oxo porphyrin, followed by a further reaction of the Mn^IV–oxo porphyrin with substrates that results in the formation of a Mn^III porphyrin complex. This result is in contrast to the oxidation of sulfides by the Mn^V–oxo porphyrin, in which the oxidation of thioanisole by the Mn^V–oxo complex produces the starting Mn^III porphyrin and thioanisole oxide. This result indicates that the oxidation of sulfides by the Mn^V–oxo species occurs by means of a two‐electron oxidation process. In contrast, a Mn^IV–oxo porphyrin complex is not capable of oxidizing sulfides due to a low oxidizing power in basic aqueous solution.     

A dinuclear iron complex based on parallel malonate binding sites: cooperative activation of dioxygen and biomimetic ligand oxidation

A ligand that offers two parallel malonate binding sites linked by a xanthene backbone, namely, Xanthmal2-, has been utilised to synthesise dinuclear FeII complex [Fe2(Xanthmal)2] (1). The reactivity of 1 in contact with O2 was investigated at -40 degrees C and room temperature. After activation of O2 through interaction with both iron centres the ligand is oxidised: at the Calpha position monooxygenation and peroxide formation occur, partially accompanied by C-C bond cleavage to yield alpha-keto ester groups. To reveal mechanistic details investigations concerning 1) peroxide decomposition, 2) the reactivity of a corresponding mononuclear complex, 3) the influence of monooxygenation of the ligand on the reactivity and 4) product formation in dependence on time were carried out. The results can be explained by postulating formation of high-valent Fe intermediates and ligand-to-metal electron transfer, and the mechanistic scheme derived includes several steps that mimic the (suggested) functioning of non-heme iron enzymes. In agreement with this proposal, ligand oxidation can also be performed catalytically. Furthermore, we show that via a competitive route [(Xanthmal)2Fe2O] (2) is formed, which is unreactive towards O2 and thus is a dead end with respect to ligand oxidation. Both compounds 1 and 2 were fully characterised, and their properties are discussed.     

Xanthene-modified and hangman iron corroles

Iron corroles modified with a xanthene scaffold are delivered from easily available starting materials in abbreviated reaction times. These new iron corroles have been spectroscopically examined with particular emphasis on defining the oxidation state of the metal center. Investigation of their electronic structure using (57)Fe Mo?ssbauer spectroscopy in conjunction with density functional theory (DFT) calculations reveals the non-innocence of the corrole ligand. Although these iron corroles contain a formal Fe(IV) center, the deprotonated corrole macrocycle ligand is one electron oxidized. The electronic ground state of these complexes is best described as an intermediate spin S = 3/2 Fe(III) site strongly antiferromagnetically coupled to the S = 1/2 of the monoradical dianion corrole [Fe(III)Cl-corrole(+?)]. We show here that iron corroles as well as xanthene-modified and hangman xanthene iron corroles are redox active and catalyze the disproportionation of hydrogen peroxide via the catalase reaction, and that this activity scales with the oxidation potential. The meso position of corrole macrocycle is susceptible toward nucleophilic attack during catalase turnover. The reactivity of peroxide within the hangman cleft reported here adds to the emerging theme that corroles are good at catalyzing two-electron activation of the oxygen-oxygen bond in a variety of substrates.     

9,9-二[4-(4-羧基苯氧基)苯基]呫吨的合成

在碘化亚铜、四丁基溴化铵和磷酸钾存在下,9,9-二(4-羟基苯基)呫吨(1)和4-甲基碘苯(2)于N,N-二甲基甲酰胺溶剂中发生Ullmann偶联反应,加热回流反应24 h,以95%的产率合成了中间体--9,9-二[4-(4-甲基苯氧基)苯基]呫吨(3),继而加入催化量的N-溴代丁二酰亚胺并在光照条件下,将中间体3氧化得到一种新型芳香族二羧酸--9,9-二[4-(4-羧基苯氧基)苯基]呫吨(4),其产率为84%,二步反应总收率为79.8%。 目标化合物4经1H NMR、13C NMR、IR和元素分析测试技术确定了其结构。 该法具有原料易得,操作简单,反应条件温和,收率高等优点。     

Water oxidation by a ruthenium complex with noninnocent quinone ligands: possible formation of an O-O bond at a low oxidation state of the metal

Tanaka and co-workers reported a novel dinuclear Ru complex, [Ru2(OH)2(3,6-Bu2Q)2(btpyan)](SbF6)2 (3,6-Bu2Q = 3,6-di tert-butyl-1,2-benzoquinone, btpyan = 1,8-bis(2,2':6',2'-terpyrid-4'-yl)anthracene), that contains redox active quinone ligands and has an excellent electrocatalytic activity for water oxidation when immobilized on an indium-tin-oxide electrode (Inorg. Chem., 2001, 40, 329-337). The novel features of the dinuclear and related mononuclear Ru species with quinone ligands, and comparison of their properties to those of the Ru analogues with the bpy ligand (bpy = 2,2'-bipyridine) replacing quinone, are summarized here together with new theoretical and experimental results that show striking features for both the dinuclear and mononuclear species. The identity and oxidation state of key mononuclear species, including the previously reported oxyl radical, have been reassigned. Our gas-phase theoretical calculations indicate that the Tanaka Ru-dinuclear catalyst seems to maintain predominantly Ru(II) centers while the quinone ligands and water moiety are involved in redox reactions throughout the entire catalytic cycle for water oxidation. Our theoretical study identifies [Ru2(O2(-))(Q(-1.5))2(btpyan)](0) as a key intermediate and the most reduced catalyst species that is formed by removal of all four protons before four-electron oxidation takes place. While our study toward understanding the complicated electronic and geometric structures of possible intermediates in the catalytic cycle is still in progress, the current status and new directions for kinetic and mechanistic investigations, and key issues and challenges in water oxidation with the Tanaka catalyst (and its analogues with Cl(-) or NO(2-)substituted quinones and a species with a xanthene bridge instead an antheracene) are discussed.     

Oxo complexes of high-valence iron in oxidation catalysis

This review deals with oxo complexes of high-valence iron (oxoferryl, or simply ferryl complexes), which play an important role in the selective oxidation of hydrocarbons and other organic compounds. The efficiency and high selectivity of natural oxygenases stimulates researchers to design chemical analogues of these systems. Since the advantages of biological and biomimetic oxidation are due to the participation of ferryl intermediates, we will consider the ways of obtaining relatively stable oxo complexes of high-valence iron and their geometric and electronic structure and reactivity.     

The role of triplet states in dye sensitization of ZnO electrodes

The quantum efficiency of photooxidation of a number of xanthene dyes at ZnO single crystal electrodes has been found to depend on the solution concentration of a triplet quenching agent, FeCN^4?₆, providing evidence for triplet state participation in the oxidation reaction.     

Reaction of Nitro-Substituted Donor-Acceptor Cyclopropanes with Pyrazoles in DMSO: Unexpected Formation of Tandem Kornblum-Type Ring-Opening Oxidation/Aza-Michael Addition Products

The ring-opening reaction of nitro-substituted donor-acceptor cyclopropanes with pyrazoles in DMSO was investigated. Unexpectedly, the cyclopropanes underwent Kornblum-type ring-opening oxidation with DMSO to form aroylmethylidene malonates as intermediates in the reactions. The intermediates further underwent aza-Michael addition with pyrazoles in tandem manner to give the corresponding aza-Michael adducts. The highlights of the methodology include the occurrence of ring-opening/oxidation under neutral conditions with DMSO and formation of aza-Michael adducts with pyrazoles under catalyst-free conditions.     

Intramolecular AR--O--AR bond formation in calixarenes

The formal dehydration of two vicinal phenol moieties of p-tert-butylcalix[6]arene was achieved in two steps by mild oxidation of the calixarene followed by treatment of the resulting monospirodienone derivative (9c) with an ionic hydrogenation mixture (Et(3)SiH/CF(3)COOH). Reaction of 9c yielded the unsubstituted xanthenocalix[6]arene 11d, while treatment of the monospirodienone derivative of a spherand-type calixarene (13) with Et(3)SiH/CF(3)COOH afforded the dibenzofuran derivative 15. The formation of the latter product indicates that, at least for 13, the rings forming the Ar--O--Ar bond in the product are not those connected by the spiro bond in the starting material. Methylation of the phenolic hydroxyl groups of 11d with methyl p-toluenesulfonate/K(2)CO(3) or dimethyl sulfate/base afforded its dimethyl and tetramethyl ether derivatives. The parent xanthone calix[6]arene derivative 17b was prepared by O-methylation of the phenol groups followed by CrO(3) oxidation of the xanthene methylene group and deprotection of the OH groups. McMurry coupling of calixanthone 17a afforded the dixanthylene 18. Calixarenes 11d and 15 (which possess a xanthene and dibenzofuran group, respectively) were structurally characterized by X-ray crystallography.     

A fluoresceinophane: 19,4,16‐trioxa‐1(2,10)‐anthracena‐2(1,2)‐benzenacyclohexadecaphane‐17,3(19H)‐dione

A novel macrocycle containing fluorescein, the highly fluorescent title compound, C₃₁H₃₂O₅, has a xanthene core and a benzyl unit that are planar. The latter is rotated by 72.99 (3)° from the xanthene mean plane. The C₁₁ alkyl tether and the xanthene group adopt a cage‐like structure and the xanthene adopts a quinoid‐type configuration. The compound crystallizes as a racemic mixture with one molecule of each isomer per unit cell. Even though the planes described by the xanthene and the benzene rings of different molecules are separated by 3.341 (4) and 3.73 (1) Å, respectively, there is insufficient overlap between the aryl units to promote π‐stacking.     

Synthesis of pyrrolo- and pyrido[1,2-a]xanthene [1,9-de]azepines: a study of the azepine ring construction

Pentacyclic pyrrolo- and pyrido[1,2-a]xanthene[1,9-de]azepines were synthesized in various oxidation states by assembling the azepine ring following two strategies: 7-endo-trig cyclization of the aryl radical derived from a gamma-methylene lactam and cyclodehydration of aldehydes. Other strategies examined (Heck reaction and intramolecular acylation) did not afford azepines, but six-membered nitrogenated rings.