Direct hydroxylation of substituted benzenes to phenols with air and CO using molybdovanadophosphates as a key catalyst

A direct synthetic method of cresols from toluene by hydroxylation with air using CO as a reducing agent was developed. The reaction of toluene with air (15 atm) and CO (5 atm) in the presence of catalytic amounts of H₄PMo₁₁VO₄₀·31H₂O and Pd/C in aqueous acetic acid at 120 °C for 2 h afforded a mixture of o-, m-, and p-cresols in 9.9% yield at 83% selectivity. Cresols were obtained in 19% yield by recharging air and CO under these conditions. A variety of substituted benzenes were hydroxylated by this method to give the corresponding phenol derivatives in higher selectivity.     

The hydrogenation of 9,10-dimethylanthracene by hydridopentacarbonylmanganese(I). Evidence for a free-radical mechanism

The reaction of 9,10-dimethylanthracene with HMn(CO)₅ yields a nearly equimolar mixture of cis- and trans-9,10-dihydro-9,10-dimethylanthracene. The results of kinetic and isotropic tracer studies provide support for a free-radical mechanism in which the rate-determining step is the transfer of a hydrogen atom from HMn(CO)₅ to 9,10-dimethylanthracene.     

Evidence for formation and different evolution of tertiary rhodium alkyl intermediates under rhodium-catalyzed deuterio-(hydro)formylation of 1-(n-pyridyl)-1-phenylethenes

Deuterioformylation of the vinylidenic substrates 1-(n-pyridyl)-1-phenylethenes, in the presence of phosphine modified Rh₄(CO)₁₂ as catalyst precursor, was carried out at 100 atm of CO and D₂ (1:1), 80 °C and at partial and complete substrate conversion.The direct ²H NMR analysis of the crude reaction mixture led to the conclusion that, under these conditions, the branched alkyl rhodium intermediate is formed almost exclusively. It can: (i) β-eliminate, (ii) undergo migratory insertion on CO or (iii) oxidative addition of deuterium to various extents depending on the position of the nitrogen atom with respect to the olefinic double bond, thus accounting for the observed different chemo- and regioselectivities.     

Co2(CO)8-induced domino reactions of ethyl diazoacetate, carbon monoxide and ferrocenylimines leading to 2-(1-ferrocenyl-methylidene)-malonic acid derivatives

Novel 2-(1-ferrocenyl-methylidene)-malonic acid derivatives are obtained upon reacting ethyl diazoacetate, carbon monoxide and ferrocenylimines in the presence of Co₂(CO)₈ as catalyst under mild conditions. Presumably, the reaction involves three steps taking place in a domino fashion, (i) carbonylation of ethyl diazoacetate leading to a ketene derivative, (ii) [2+2] cycloaddition of the ketene with the ferrocenylimine present in the reaction mixture resulting in the formation of a β-lactam and (iii) N(1)-C(4) cleavage of the β-lactam ring. In most cases, 2-(1-ferrocenyl-methylidene)-malonic acid derivatives are obtained as a separable mixture of E- and Z-isomers in ratios depending on the structure of the imine component.     

Preparation of Ru(CO)3(PMe3)MeI and its acetyl derivatives

[Ru(CO)₄PMe₃] reacts with MeI to give fac-[Ru(CO)₃(PMe₃)(Me)I]. The latter reacts with PMe₃ to give a mixture of the three isomers of cis-bis(trimethylphosphine)-cis-dicarbonyl acetyl iodide [Ru(CO)₂(PMe₃)₂(COMe)I]. Decarbonylation of the mixture gives only the trans-bis(trimethylphosphine)-cis-dicarbonyl methyl iodide complex [Ru(CO)₂(PMe₃)₂MeI], which was also prepared by oxidative addition of MeI to [Ru(CO)₃(PMe₃)₂].     

Surface organometallic chemistry: Reductive carbonylation of OsCl3·3H2O supported on silica

The reductive carbonylation of silica-supported OsCl₃·3H₂O was investigated under atmospheric pressure of CO or of a mixture of CO and H₂O at relatively mild temperatures. Starting from OsCl₃·3H₂O a mixture of physisorbed α-[Os(CO)₃Cl₂]₂, cis-[Os(CO)₄Cl₂] and a species bound to the surface silanol groups, [Os(CO)₃Cl₂(HOSi)], is formed working at 100°C under CO. At higher temperatures [Os(CO)₃Cl₂(HOSi)] is the major surface species. Attempts to reduce further on the surface these Os^II chlorocarbonyl species failed due to their easy sublimation and to the difficult removal of the chloro ligands. However, when the silica is treated with a weak base such as NaHCO₃, α- or β-[Os(CO)₃Cl₂]₂ supported on silica may be reduced with CO to [Os₃(CO)₁₂], with CO and H₂O to a mixture of [OS₃(CO)₁₂] and [H₄Os₄(CO)₁₂], and finally with H₂ to [H₄Os₄(CO)₁₂]. These reduction processes occur via the anchored [Os(CO)₃(OSi)₂]_n species, as intermediate surface species.     

Olefin hydrocarboxylation under mild conditions in nickel complex solutions

The hydrocarboxylation of α-olefins into carboxylic acids can be carried out in the presence of the dissolved complex NiCl₂(PPh₃)₂ at comparatively low CO pressures (below 0.8 MPa) with a fairly high product yield. Hexene-1 in acetic acid is converted into a mixture of heptanoic and 2-methylhexanoic acids, whose total yield is 40%. The molar ratio of the isomers is close to unity. However, the normal-chain product dominates at low CO pressures. Under the conditions examined, the catalyst is active only in the presence of a hydrogen (hydride ion) donor. The activity of the nickel complex can be markedly enhanced by preexposure of the reaction mixture to hydrogen pressure in the absence of CO. For the 0.8 MPa CO + 3.2 MPa H₂ gas mixture at 170°C, the turnover frequency of the catalyst is 28.5 and its activity is 4.8 h^?1.     

Synthesis and some reactions of a 2,2′-biphospholyl

1,1′-Diphenyl-3,3′,4,4′-tetramethyl-2,2′,5,5′-tetrahydro-2,2′-biphosphole obtained by reductive dimerization of the appropriate phosphole has been converted into the corresponding 2,2′-biphosphole by P-bromination followed by dehydrobromination of the resulting P,P′-tetrabromo compound with α-picoline. This 2,2′-biphosphole gives two isomeric P-sulfides upon reaction with sulfur, and a Mo(CO)₄ chelate upon reaction with Mo(CO)₆. Cleavage of the two P-phenyl bonds by lithium in THF yields the corresponding biphospholyl anion, which is converted into a mixture of two isomeric bis(η⁵,η⁵-2,2′-diphosphafulvalene)diirons by treatment with FeCl₂. The reaction of Mn₂(CO)₁₀ in boiling xylene affords a mixture of three complexes, including a (η⁵,η⁵-2,2′-diphosphafulvalene)hexacarbonyldimanganese produced by thermal cleavage of the two PPh bonds. Under CO pressure there is a [1,5] P → C shift of the two phenyl groups, leading to formation of (η⁵,η⁵-3,3′-diphenyl-2,2′-diphosphafulvalene)hexacarbonyldimanganese.     

Metallcarbonyl-synthesen : V. Die reduktive hochdruckcarbonylierung von (η5-C5H5)NbCl4 als einfache und leistungsfähige synthesemethode für (η5-C5H5) Nb(CO)4. Darstellung der isotopenmarkierten derivate (η5-C5H5) Nb(CO)4 − n(13CO)n und (η5-C5H5) Nb(CO)4 − n(13C18O)n

The reductive high-pressure carbonylation of tetrachloro(η⁵-cyclopentadienyl)niobium using sodium as reduction agent and Cu/Al mixture as halogen acceptor system cleanly yields tetracarbonyl (η⁵-cyclopentadienyl)niobium which can be synthesized by means of this new procedure on a 35 g-scale, with yields ranging between 89 and 94%. Under photolysis conditions, (η⁵-C₅H₅) Nb(CO)₄ is converted into the solvent complex (η⁵-C₅H₅) Nb(CO)₃THF which, in turn, incorporates ¹³Co or ¹³C¹⁸O under mild conditions to give the labelled derivatives (η⁵-C₅H₅) Nb(CO)_{4 ? n}(¹³CO)_n and (η⁵-C₅H₅) Nb(CO)_{4 ? n}(¹³C¹⁸O)_n, respectively.     

Metalloporphyrins as chemical shift reagents: the unambiguous NMR characterization of the cis- and trans-isomers of meso-(bis)-4′-pyridyl-(bis)-4′-carboxymethylphenylporphyrins

The condensation of pyrrole with 4-pyridylcarboxyaldehyde and methyl 4-formyl benzoate under Adler-Longo conditions yielded the series of meso-(4′-pyridyl)/(4′-carboxymethylphenyl)porphyrins as a mixture. Careful column chromatography afforded each isomer in pure form. In this paper we focus on the two bis-substituted isomeric meso-porphyrins, 5,10-bis(4′-pyridyl)-15,20-bis(4′-carboxymethylphenyl)porphyrin and 5,15-bis(4′-pyridyl)-10,20-bis(4′-carboxymethylphenyl)porphyrin, respectively, 4′-cis and 4′-transDPyDMeP. The assignment of the geometry of the two isomers was performed by ¹H NMR spectroscopy on the trinuclear adducts [(4′-cisDPyDMeP){Ru(TPP)(CO)}₂] and [(4′-transDPyDMeP){Ru(TPP)(CO)}₂], obtained by selective coordination of [Ru(TPP)(CO)(EtOH)] (TPP=tetraphenylporphyrin) to the peripheral nitrogen atoms. The axially bound ruthenium porphyrins act as chemical shift reagents on the central porphyrin, allowing a clear distinction of the pyrrole proton resonances and consequent unambiguous assignment of the geometry of each isomer based upon symmetry considerations.     

A new cobalt carbonyl-carbon disulphide cluster containing a Co3C and a Co3S pyramid symmetrically linked by a CS2-bridge: sym-SCo6(CO)16C(CS2)

sym-(CO)₉Co₃C(CS₂)Co₃(CO)₇S has been isolated from the mixture formed in the reaction of Co₂(CO)₈ with CS₂. This is the fifth member of the C_mS_nCo_p(CO)_q family identified by X-ray diffraction studies. The molecular structure of the title compound is discussed and briefly compared with that of the asymmetric isomer and related compounds.     

Relaxation of the individual vibrational levels of carbon monoxide following shock heating at 2100 K

The increases in the populations of the vibrational levels v = 1 to v = 5 in CO which is undergoing thermal vibrational relaxation at 2100 K have been monitored using a cw CO laser. The experiments have been carried out in a very narrow temperature range for mixtures of CO, Ar and He. Under these conditions the first part of the relaxation region is clearly visible, and it has been possible to compare the population growths of different vibrational levels under the same conditions. We have shown that the curve for the increase in the population of the level v = 1 with time is clearly different from those of the higher levels. It has been shown that all of the vibrational levels studied in this work on CO relax with a common vibrational temperature, as postulated in the model of Shuler and co-workers. The results reported here are qualitatively different from those presented by Chow and Greene on HI.     

Ruthenium-catalyzed reduction of racemic tricarbonyl(η-aryl ketone)chromium complexes using transfer hydrogenation: A simple alternative to the resolution of planar chiral organometallics

Racemic planar chiral (η⁶-aryl ketone)Cr(CO)₃ complexes (aryl ketone = 1-indanone, 1-tetralone, 4-chromanone and thiochroman-4-one) were prepared by refluxing the aryl ketone with Cr(CO)₆ in a 10:1 mixture of dibutyl ether and THF. The reductions of the organometallic ketones by transfer hydrogenation in 2-propanol containing KOH and the catalyst precursor, generated from [RuCl₂(η⁶-benzene)]₂ and (−)-ephedrine, resulted in optically active syn-(R,S)-(η⁶-aryl alcohol)Cr(CO)₃ and (R)-(η⁶-aryl ketone)Cr(CO)₃ compounds in 31-97% ee. Reduction of racemic (η⁶-thiochroman-4-one)Cr(CO)₃ with the catalyst precursor generated from (+)-norephedrine, instead of (−)-ephedrine, inverted the configuration of the products obtained. Syn-(S,R)-(η⁶-thiochroman-4-ol)Cr(CO)₃ and (S)-(η⁶-thiochroman-4-one)-Cr(CO)₃ were isolated in 49% and >95% ee, respectively. The free aryl ketones were reduced using the same conditions as their respective chromium complexes, giving aryl alcohols in high ee (>95%). Reactions of non-rigid acetophenone, propriophenone and their tricarbonylchromium complexes resulted in moderate to low ee.     

Coordination complexes containing multidentate ligands : V. The reactions between trans-carbonylchlorobis(triphenylphosphine)iridium and trans-carbonylchloro(triphenylarsine)iridium and some tridentate group VB ligands

Bis[3-(dimethylarsino)propyl]phenylarsine, (tas), reacts with trans-Ir(CO)(EPh₃)₂ X (E = P, As; X = F, Cl, Br, I) to yield the (Ir(CO)(tas)] X complexes. In contrast, the similar ligand bis[3-(dimethylarsino)propyl]phenylphosphine, (dap), reacts with trans-Ir(CO)(EPh₃)₂X (E = P, As; X = Cl, Br, I) to yield a mixture of [Ir(CO)(dap)X] and [Ir(CO)(dap)]X, and with trans Ir(CO)(EPh₃)₂F (E = P, As) to yield solely [Ir(CO)(dap)F]. The cations [Ir(CO)(L)]⁺ (L = tas, dap) readily yield tetraphenylborate derivatives, [Ir(CO)(L)]BPh₄. The oxygenation of [Ir(CO)(tas)]⁺ in solution proceeds almost to completion after 15 h, whereas [Ir(CO)(dap)]⁺ does not appear to undergo oxygenation.     

Rhodium catalyzed deuteroformylation of styrene: (E)- and (Z)-β-deuterostyrene and β,β-dideuterostyrene formation via selective β-hydride elimination from the branched alkylrhodium intermediate

Deuteroformylation of styrene in the presence of Rh₄(CO)₁₂ as a catalytic precursor was carried out at 160 atm of CO and D₂ 1/1 at two temperatures (20 and 90°C) and for times yielding partial or complete conversion. Compounds recovered from the mixture produced by reaction and partial conversion at 90°C include unlabeled styrene, (E)- and (Z)-β-deuterostyrene, C₆H₅CHCHD, and β,β-dideuterostyrene, C₆H₅CHCD₂, whereas at room temperature the styrene does not take up deuterium. These results indicate that under hydroformylation conditions the branched alkylrhodium intermediate, which affords the branched aldehyde, in part dissociates into rhodium hydride and deuterated olefin. By contrast the linear alkyl intermediate does not dissociate under the same conditions, but instead yields almost completely the corresponding aldehyde.     

Isolation of the first neutral chromium formyl derivatives

The first neutral chromium formyl derivative Cp* Cr(CO)₂[P(OMe)₃](CHO) has been obtained as a cis-trans isomers mixture. Both of the isomers, which are remarkably thermally stable, slowly decompose in solution, at different rates, to give cis-Cp*Cr(CO)₂ [P(OMe)₃]H.     

Experimental and kinetic modeling study of the effect of NO and SO2 on the oxidation of CO?H2 mixtures

The effect of NO and SO₂ on the oxidation of a CO? H₂ mixture was studied in a jet‐stirred reactor at atmospheric pressure and for various equivalence ratios (0.1, 1, and 2) and initial concentrations of NO and SO₂ (0–5000 ppm). The experiments were performed at fixed residence time and variable temperature ranging from 800 to 1400 K. Additional experiments were conducted in a laminar flow reactor on the effect of SO₂ on CO? H₂ oxidation in the same temperature range for stoichiometric and reducing conditions. It was demonstrated that in fuel‐lean conditions, the addition of NO increases the oxidation of the CO? H₂ mixture below 1000 K and has no significant effect at higher temperatures, whereas the addition of SO₂ has a small inhibiting effect. Under stoichiometric and fuel‐rich conditions, both NO and SO₂ inhibit the oxidation of the CO? H₂ mixture. The results show that a CO? H₂ mixture has a limited NO reduction potential in the investigated temperature range and rule out a significant conversion of HNO to NH through reactions like HNO + CO ?? NH + CO₂ or HNO + H₂ ?? NH + H₂O. The chain terminating effect of SO₂ under stoichiometric and reducing conditions was found to be much more pronounced than previously reported under flow reactor conditions and the present results support a high rate constant for the H + SO₂ + M ?? HOSO + M reaction. The reactor experiments were used to validate a comprehensive kinetic reaction mechanism also used to simulate the reduction of NO by natural gas blends and pure C₁ to C₄ hydrocarbons. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 564–575, 2003     

Formation of acetaldehyde via photocarbonylation of methane with CO

Direct photocarbonylation of methane to give acetaldehyde occurred when a mixture of methane and CO dissolved in benzene was subjected to UV irradiation at λ < 290 nm. The reaction was accelerated by rhodium RhCl(CO)(PR₃)₂ complexes, where R = alkyl, Ph, or OPh.     

Carbon monoxide isotope enrichment and separation by pressure swing adsorption

Simulations of three different 3-bed 3-step pressure swing adsorption (PSA) cycles were carried out to study the enrichment and recovery of ¹⁴CO from an isotopic mixture of ¹⁴CO, ¹³CO and ¹²CO using NaX zeolite. Each PSA cycle included feed pressurization/feed (FP/P), heavy reflux (HR) and countercurrent depressurization (CnD) steps; they differed only in the way the CnD step was carried out: PSA Cycle I was carried out under total reflux (i.e., with no ¹⁴CO heavy product production); PSA Cycle II was carried out with discontinuous ¹⁴CO heavy product production; and PSA Cycle III was carried out with continuous ¹⁴CO heavy product production. The effects of the CnD step valve coefficient (c _v ), heavy reflux ratio (R _R ), and cycle time (t _cyc ) on the PSA process performance were determined in terms of the ¹⁴CO enrichment, ¹⁴CO recovery and CO feed throughput. The results showed that there was essentially no limit to the extent of the ¹⁴CO enrichment, despite the inherently low ¹⁴CO/¹²CO (1.05) and ¹⁴CO/¹³CO (1.12) separation factors for these isotopes on NaX zeolite. Under total reflux an optimum c _v was found for the CnD step and ¹⁴CO enrichments as high as 152 were obtained. Using the optimum c _v under finite reflux, a ¹⁴CO enrichment approaching 20 and a ¹⁴CO recovery approaching 100 % were easily achieved with discontinuous (PSA Cycle II) or continuous (PSA Cycle III) ¹⁴CO heavy product production. There was essentially no difference in the performance of PSA Cycles II and III, a counterintuitive result. The ¹⁴CO enrichment and the ¹⁴CO recovery both increased with decreasing CO feed throughputs and higher R _R , which were always very close to unity.     

Übergangsmetall-Carbin-Komplexe: CI. Gezielter Aufbau eines Diethylaminocarbin-Liganden am Wolfram aus Ethylisocyanid-Vorstufen

An effective route to the W⁰-diethylaminocarbyne complex Cp(CO)(EtNC)WCNEt₂ (5) (Cp = η⁵C₅H₅) is reported starting from the easily accessible, isomeric mixture of the W^II-isocyanide compounds cis- and trans-CpW(CO)₂(EtNC)I (1a, 1b). Thus oxidative decarbonylation of 1a/1b with one equivalent of I₂ results in the quantitative formation of the W^IV complex CpW(CO)(EtNC)(I)₃ (2). Subsequent reductive elimination of two iodide ligands in 2 with Na/Hg leads in the presence of EtNC to an isomeric mixture of the W^II-compounds cis- and trans-CpW(CO)(EtNC)₂I (3a, 3b), the formal carbonyl substitution products of 1a and 1b, in high yield, Further reduction of 3a/3b is achieved with Na powder and yields the electron-rich W⁰-metallate Na[CpW(CO)EtNC)₂] (4) in quantitative yield. Finally ethylation of 4 with Et₃OBF4 occurs exclusively at the isocyanide-nitrogen and affords the desired complex 5.