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A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

2,5-Disubstituted-1,3,4-oxadiazoles are prepared in excellent yields (up to 97%) under totally solvent-free conditions by the quantitative formation of N-acylhydrazone from the reaction of a hydrazide with an aldehyde using a ball-mill for 10 min at room temperature followed by oxidation with BTI at 80°C for 1h.

Aqueous amines are currently the most promising solution for large-scale CO_2 capture from industrial sources. However, molecular design and optimization of amine-based solvents have proceeded slowly due to a lack of understanding of the underlying reaction mechanisms. Unique and unexpected reaction mechanisms involved in CO_2 absorption into aqueous hydrazine are identified using ^1H, ^(13)C, and ^(15)N NMR spectroscopy combined with first-principles quantum-mechanical simulations. We find production of both hydrazine mono-carbamate (NH_2-NH-COO^−) and hydrazine di-carbamate (^−OOC-NH-NH-COO^−), with the latter becoming more populated with increasing CO_2 loading. Exchange NMR spectroscopy also demonstrates that the reaction products are in dynamic equilibrium under ambient conditions due to CO_2 exchange between mono-carbamate and di-carbamate as well as fast proton transfer between un-protonated free hydrazine and mono-carbamate. The exchange rate rises steeply at high CO_2 loadings, enhancing CO_2 release, which appears to be a unique property of hydrazine in aqueous solution. The underlying mechanisms of these processes are further evaluated using quantum mechanical calculations. We also analyze and discuss reversible precipitation of carbamate and conversion of bicarbonate to carbamates. The comprehensive mechanistic study provides useful guidance for optimal design of amine-based solvents and processes to reduce the cost of carbon capture. Moreover, this work demonstrates the value of a combined experimental and computational approach for exploring the complex reaction dynamics of CO_2 in aqueous amines.

Aqueous amines are currently the most promising solution for large-scale CO

Hydrazine, which is the simplest diamine, was investigated for its viability as a sorbent for carbon dioxide (CO2) capture from flue gas using lab scale experiments. It has a high CO2 absorption capacity due to its low molecular weight. The overall mass transfer coefficient of aqueous hydrazine (32 wt%) is about 2.9 times higher than that of the benchmark monoethanolamine (MEA, 30 wt%), indicating that the absorption rate of CO2 in aqueous hydrazine is remarkably fast. Furthermore, the cyclic capacity of aqueous hydrazine is comparable to that of MEA. Aqueous hydrazine has demonstrated the ability to capture and release CO2 for three cycles without changing its absorption capacity. In addition, aqueous hydrazine does not show any indication of thermal degradation up to 90 °C. These advantages could lead to a substantial reduction of the cost of electricity, making aqueous hydrazine a promising new sorbent for post-combustion CO2 capture applications.

The synthesis of hollow nickel-coated silica microspheres containing rhodium nanoparticles (NPs) (Rh/Ni@SiO2) via thermal hydrolysis of urea using core–shell silica microspheres as templates is described. This dissolution-and-deposition method using urea as a precipitating agent provided uniform hollow microspheres composed of amorphous Ni(OH)2 and silica (SiO2) layers along with small amounts of Rh species even without etching; these hollow microspheres transformed to crystalline Rh/Ni@SiO2 microspheres after annealing at 750 °C under a reducing atmosphere. The formation of a hollow structure is dependent on the concentration of urea and unique dissolution behavior of the core–shell silica. The bimetallic Rh/Ni@SiO2 microsphere with a low Rh content (6.35 wt%) is a highly active catalyst for complete dissociation of hydrous hydrazine into hydrogen and nitrogen. Complete release of hydrogen from hydrous hydrazine was accomplished at 25 °C with a H2 selectivity of 99.4% and turnover number of 66. The used Rh/Ni@SiO2 catalyst, which was recovered by a magnet, was reused in subsequent reactions with virtually identical activity.

Many amines are liquid and their handling is inconvenient compared with the corresponding solids. We transformed a liquid (S)-(−)-1-phenylethylamine 1 to the corresponding neutral solid form 2 by reacting with carbon dioxide. We performed reductive amination of 2 with various aldehydes 3 under solvent-free conditions to provide secondary amines 5 in high yields.

An aqueous conductive ink of multi-walled carbon nanotubes (MWCNTs) for inkjet printing was formulated. To prepare the homogeneous MWCNT ink in a size small enough not to block a commercial inkjet printer nozzle, we used a kinetic ball-milling process to disperse the MWCNTs in an aqueous suspension with naphthyl-group-based non-ionic surfactants. When a patterned electrode was overlaid by repeated inkjet printings of the ink on various types of paper, the sheet resistance decreased rapidly following a power law, reaching approximately 760 Ω/sq, which is the lowest value ever for a dozen printings. Hall effect measurements at various magnetic fields and temperatures showed that the printed MWCNT paper electrode exhibited excellent semi-metallic conductivity with a p -type extrinsic semiconductive behavior such that the temperature-dependent resistivity was dominantly affected not by the lattice phonon scattering related to the mobility but by the charge impurity scattering related to the concentration of doped impurities. The Raman and Fourier transform infrared spectra revealed that the oxidation of the MWCNTs was the source of the doped impurities.

Azines, pyrazoles, and pyridazinones were isolated as the sole products in high yields (>97%) by grinding solid hydrazine (H3N + NHCO2 � ) with di-carbonyl compounds or by their reaction in the absence of sol- vent. Neither catalysts nor additives were needed to promote the reactions. The solid-state and sol- vent-free reactions proceeded under ambient conditions and did not produce any wastes other than water and carbon dioxide. They are operationally easy, environmentally safe, and readily scalable, allow- ing for highly selective synthesis of compounds containing the hydrazine motif.

Highly conjugated azines were prepared by solid state grinding of solid hydrazine and carbonyl compounds such as aldehydes and ketones, using a mortar and a pestle. Complete conversion to the azine product is generally achieved at room temperature within 24 h, without using solvents or additives. The solid-state reactions afford azines as the sole products with greater than 97% yield, producing only water and carbon dioxide as waste.

Department of Chemistry, Pohang University of Science and Technology, Pohang 790-784, KoreaReceived December 13, 2010, Accepted January 5, 2011Key Words : Aluminum oxyhydroxide, Aromatic halides, Dehalogenation, Pd nanoparticles, Solvent-free re-actionThe dehalogenation of aromatic halides possesses greatsignificance not only in the removal of halogenated organiccontaminants but also in the development of syntheticmethodologies.

A novel one-pot process that can produce freestanding reduced graphene oxide (RGO) sheets in large scale through a mechanochemical method is presented, which is based on a 1:1 adduct of hydrazine and carbon dioxide (H_3N^+NHCO_2^−, solid hydrazine). We were able to synthesize RGO sheets by grinding solid hydrazine with graphene oxide (GO), followed by storing the mixed powder at 50 °C for 10 min. No solvents, nor large vessels, nor post-annealing at high temperatures are required. The resulting RGO sample was characterized by elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Brunauer–Emmett–Teller measurement, thermo gravimetric analysis, Fourier transform infrared spectroscopy, solid state nuclear magnetic resonance spectroscopy, and conductivity measurement. It exhibits excellent conductivity and possesses a high specific surface area. This reduction method was successfully applied for the fabrication of inkjet-printed RGO devices on a flexible substrate.

Solid alkenes and aromatic nitro compounds are readily hydrogenated to the corresponding alkanes without further reduction of other functional group and amino compounds in nearly quantitative yields in the presence of Pd nanoparticles entrapped in aluminum oxy-hydroxide under the solvent-free condition.

Reactions of [Cp*Ir(η3-CH2CHCHPh)(NCMe)]OTf (1) with protic amines, alcohols, and water produce amidine complexes [Cp*Ir(η3-CH2CHCHPh)(NHC(NR2)Me)]OTf (2) (R2 = (Me)2 (a), (Me)(H) (b), (i-Pr)(H) (c), (−CH2(CH2)3CH2−) (d)), imino−ether complexes [Cp*Ir(η3-CH2CHCHPh)(NHC(OR‘)Me)]OTf (4) (R‘ = Me (a), Et (b), i-Pr (c)), and amido complex Cp*Ir(η3-CH2CHCHPh)(NHC(O)Me) (5-K), respectively. The keto form amido complex 5-K undergoes tautomerization to give the enol form complex Cp*Ir(η3-CH2CHCHPh)(NC(OH)Me) (5-E) in polar solvents. Tertiary amines (NMe3, NEt3) react with 1 in chlorinated solvents (XCl) to give the chloro complex Cp*IrCl(η3-CH2CHCHPh) (3) and quaternary ammonium salts [R3NX]OTf (R = Me, Et and X = CH2Cl, CH3, CHCl2, CCl3, PhCH2). Crystal structures of 2a, 4a, 5-K, and [Cp*Ir(NHC(OH)Me)(OH2)(PPh3)]OTf2 (6) have been determined by single-crystal X-ray diffraction analysis, which lead us to suggest hybrid structures, Ir−-NH−C(N+Me2)Me (2a‘) for 2a and Ir−-NH−C(O+Me)Me (4a‘) for 4a to some extent. Co...

Active, paper-based, microfluidic chips driven by electrowetting are fabricated and demonstrated for reagent transport and mixing. Instead of using the passive capillary force on the pulp to actuate a flow of a liquid, a group of digital drops are transported along programmed trajectories above the electrodes printed on low-cost paper, which should allow point-of-care production and diagnostic activities in the future.

Solid hydrazinium carboxylate reacts with α, β, or γ-diketo compounds under neat conditions A) or B).

The rhodium(I) complex, [Rh(COD)Cl]2, intercalated into montmorillonite, is an effective catalyst for the selective hydroformylation of allyl acetate derivatives to produce the corresponding linear or branched aldehydes. The catalytic reaction of allyl acetates gave linear aldehydes with high selectivity at temperatures > 130°C, while the branched aldehyde could be obtained as the major product, at lower temperature (< 50°C), and in excellent yield.

The hydroesterification of vinylsilanes, catalyzed by a palladium complex intercalated into montmorillonite, in the presence of an appropriate amount of triphenylphosphine and p-toluenesulfonic acid, afforded β-silyl esters in high yield with excellent regioselectivity. The hydroesterification reaction of trimethylvinylsilane in the presence of a diol gives the monoesterification product in a selective manner.

Various solid carbamates were prepared from the reactions of liquid amines with carbon di- oxide in an autoclave and these carbamates were used as stable, efficient alternatives for toxic liquid amines. Solid-state grinding of carbamates and alde- hydes, using a mortar and pestle, produced imines as the sole products in greater than 97% yields. Complete conversions were generally accomplished within a day at 258C without using solvents or addi- tives. Reaction rates were drastically enhanced upon increasing the reaction temperature. In con- trast, reactions of aldehydes with liquid amines in the presence of solvent or in neat conditions afford- ed imines in moderate yields along with by-prod- ucts.

The selective hydrogenation of the double bond of vinyl epoxides is catalyzed by either the species generated by treatment of the binuclear palladium complex, [(But2PH)PdPBut2]2 with oxygen, or by the cationic iridium(I) complex, [Ir(COD)(PPh3)(PhCN)]BF4, to produce the corresponding saturated epoxides at room temperature, and with good selectivity.

Catalytic hydrogenation of fused heteroaromatic compounds, acridine, quinoline and quinaldine, selectively occurs at the nitrogen containing rings to give 9,10-dihydroacridine, 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroquinaldine in the homogeneous solution prepared from the reaction of [Ir(COD)(PPh3)(PhCN)]ClO4 (COD=1,5-cyclooctadiene) with H2 (5 atm) at 50°C, while isoquinoline and indole are not hydrogenated under the same experimental conditions. In the presence of the rhodium analog [Rh(COD)(PPh3)(PhCN)]ClO4 however, both isoquinoline and indole are also hydrogenated at the nitrogen containing rings, which is understood in terms of heterogeneous catalysis by metallic rhodium powders produced in the reduction of the rhodium compound under the same experimental conditions (50°C, 5 atm of H2).

The iridium(O) carbonyl cluster, Ir4(CO)12 (1), and rhodium(O) carbonyl cluster, Rh6(CO)16 (2), were prepared from the reactions of [Ir(COD)(PhCN)2]BF4 (3) and [Rh(COD)(PhCN)2]BF4 (4) (COD = 1,5-cyclooctadiene) with CO (2 atm) and H2 (7 atm) at 100 °C in high yield (>95 %).

The reaction proceeds by solid state grinding of a hydrazine and aldehydes or ketones to afford the conjugated azines with < 97% yield.

The zwitterionic form of carbazic acid is isolated as a stable solid and successfully used as a hydrazine replacement in the synthesis of azines (II) and (IV).

An effective and environmentally friendly dehalogenation of solid aromatic halides using Pd/AlO(OH) as catalyst under solvent-free conditions is developed.

Solid alkenes and aromatic nitro compounds are readily hydrogenated to the corresponding alkanes without further reduction of other functional group and amino compounds in nearly quantitative yields in the presence of Pd nanoparticles entrapped in aluminum oxy-hydroxide under the solvent-free condition.

The complexes [Rh(CO)(PPh3)3]ClO41 and [Ir(cod)(PhCN)(PPh3)]ClO42(cod = cycloocta-1,5-diene), rapidly catalyse the double-bond migration of 2-ethylprop-2-en-1-ol 3 and prop-2-en-1-ol 4, respectively to generate a significant amount of the enols 2-methylbut-1-en-1-ol 5 and prop-1-en-1-ol 6 in the absence of a solvent and in CD3COCD3. Both enols 5 and 6 are quite stable and slowly undergo ketonization to the corresponding carbonyl compounds at room temperature in the absence of a solvent and in aprotic solvents. Detailed 1H NMR spectral data at 300 MHz suggest that two isomers (Z and E) of compound 5 are simultaneously produced in the reaction of 3 and 1, the ratio of the isomers (major:minor) being ca. 6–9 : 1. Reaction of compound 4 with 2 also generates the Z(major) and E isomers (minor product) of 6. The Z isomer initially generated rapidly undergoes isomerization to give the E isomer in the presence of 2, while both the Z and E isomers relatively slowly undergo ketonization. Additional 1H and 13C NMR and infrared spectral data for Me2CCHOD and Me2CDCHO are reported with some experimental details.

New cationic iridium(I) complexes, [Ir(cod)(PPh3)L]ClO41[cod = cycloocta-1,5-diene; L = PhCN, PhCHCHCN, CH2CHCN, CH2C(Me)CN, MeCHCHCN or CH2CHCH2CN co-ordinated through the nitrogen atom], have been prepared by the reactions of [IrCl(cod)(PPh3)] with AgClO4 in the presence of L. Reaction of [Ir(cod)(PPh3)(PhCN)]ClO41a with H2 gives the cis-dihydridoiridium(III) complex [IrH2(cod)(PPh3)(PhCN)]ClO42a where the two hydrides are trans to PhCN and an olefinic group of cod, respectively. Complex 2a is stable both in solution and in the solid state at low temperature and decomposes at 15 °C to give cyclooctane and unidentified Ir–cod complex(es). The nitrile (L) in 1 is readily replaced by both PPh3 and CO, while cod is replaced only by CO. In the presence of complexes 1, unsaturated alcohols such as CH2CHCH2OH, CH2CHCH(Me)OH and CH2CHCH(Ph)OH rapidly undergo isomerization to the corresponding saturated carbonyl compounds at room temperature. Complex 1a catalyses the hydrogenation of unsaturated aldehydes, PhCHCRCHO (R = H, Me or Cl) to give PhCHCRCH2OH, PhCH2CHRCHO and PhCH2CHRCH2OH under H2(pH2= 6 atm) at 50 °C.

The selective hydrogenation of the double bond of vinyl epoxides is catalyzed by either the species generated by treatment of the binuclear palladium complex, [(But2PH)PdPBut2]2 with oxygen, or by the cationic iridium(I) complex, [Ir(COD)(PPh3)(PhCN)]BF4, to produce the corresponding saturated epoxides at room temperature, and with good selectivity.

Reactions of cationic iridium(I)-COD (COD = 1,5-cyclooctadiene) complexes, [Ir(COD)(PhCN)(PPh3)]ClO4 (1), [Ir(COD)(PPh3)2]ClO4 (2) and [Ir(COD)(PhCN)2]ClO4 (3) with nitriles under H2 catalytically produce primary, secondary and tertiary amines. Hydrogenation of nitriles (RCN) gives HCl salts of amines (RCH2NH2HCl, (RCH2)2NH HCl) in CH2Cl2. Secondary and tertiary amines seem to be produced by the reactions of RCN with primary and secondary amines, respectively under H2 in the presence of catalysts. The hydrogenation in the presence of1 and2 is homogeneously catalyzed by soluble iridium-PPh3 complexes formed in the reactions of1 and2 with H2 and RCN whereas the hydrogenation in the presence of3 is heterogeneous by metallic iridium powders produced in the reduction of3 by H2.

The hydrogenation of C 6 H 5 CHCHCHO ( 1 ), C 6 H 5 CHC(CH 3 )CHO ( 6 ) and C 6 H 5 CHC(Cl)CHO ( 7 ) by Ir(ClO 4 )(CO)(PPh 3 ) 2 ( 2 ), IrCl(PPh 3 ) 3 ( 8 ), IrCl(CO)(PPh 3 ) 2 ( 9 ) and [Ir(CO)(PPh 3 ) 3 ]ClO 4 ( 10 ) occurs primarily at the carbonyl group to give unsaturated alcohols, C 6 H 5 CHCHCH 2 OH ( 5 ), C 6 H 5 CHC(CH 3 ) CH 2 OH ( 11 ) and C 6 H 5 CH  C(Cl)CH 2 OH ( 12 ) at 50°C under 9 atm of hydrogen. Compound 5 is isomerized to C 6 H 5 CH 2 CH 2 CHO ( 3 ) by 2 , 8 and 9 but not by 10 . The carbonyl group of 3 is further hydrogenated to produce the saturated alcohol, C 6 H 5 CH 2 CH 2 CH 2 OH ( 4 ) in the presence of 2 , 8 and 9 . The isomerizations: 5 → 3 by 10 , and 11 → C 6 H 5 CH 2 CH(CH 3 )CHO and 12 → C 6 H 5 CH 2 CH(Cl)CHO by 8 and 9 probably do not occur for steric reasons; the interaction between the internal olefinic group and the iridium with bulky ligands is hindered.

Titanium dioxide (TiO2) nanoparticles labelled with 18O isotopes were prepared via a sol–gel method with titanium alkoxide and 18O water precursors. The presence of 18O in the labelled TiO2 sample was confirmed using Raman spectroscopy and secondary-ion mass spectrometry. The photocatalysis of cyclohexane under UV light was investigated using 18O-labelled TiO2 as the catalyst; this reaction yielded 18O-containing cyclohexanone as the major product. The 18O content in the cyclohexanone product dramatically decreased with increasing reaction time. This isotopic experiment demonstrates that the oxygen atom in cyclohexanone originates from surface oxygen in 18O-labelled TiO2. Similar photoreactions performed with toluene and para-xylene as the hydrocarbon substrates afforded oxidation products containing 18O isotopes. The migration of oxygen atoms in 18O-labelled TiO2 into liquid hydrocarbons provides direct evidence for the involvement of the solid oxide in the interfacial reaction between a liquid substrate and surface oxygen in a solid catalyst.

A dual catalyst containing Pd and CuFe(2)O(4) nanoparticles in a silica shell exhibits98% conversion of arylacetylenes to related styrenes with selectivity greater than 98%, which are better than those obtained using a commercial Lindlar catalyst. The excellent synergy was likely a result of the proximal interaction between Pd and CuFe(2)O(4) nanoparticles.

A solid hydrazine was isolated as a crystalline powder by reacting aqueous hydrazine with supercritical CO(2). Its structure determined by single crystal X-ray diffraction shows a zwitterionic form of NH(3)(+)NHCO(2)(-). The solid hydrazine is remarkably stable but is as reactive as liquid hydrazine even in the absence of solvents.

Alkynes (HCCH, PhCCH) insert into Ir–P (phosphine) and Ir–As (arsine) bonds of [Ir(H)(CCPh)(L3)(MPh3)]+ and [[graphic omitted]H)(MeCN)(L3)]+ in the presence of MPh3, to produce [Ir(H)(CCPh)(L3)(CHCHR–M + Ph3)]+ and [[graphic omitted]H)(L3(CHCHR–M+Ph3)]+[R = H, Ph; L3=(CO)(PPh3)2; M = P, As].

Reactions of cationic iridium(I) complexes, [Ir(cod)(PPh3)2]ClO41 and [Ir(cod)(PPh3)(PhCN)]ClO42(cod = cycloocta-1,5-diene) with water-swelled sodium montmorillonite have been shown to produce iridium complex-intercalated clays, [Ir(cod)(PPh3)2]+–montmorillonite 1c and [Ir(cod)(PPh3)-(PhCN)]+–montmorillonite 2c. Compounds 1c and 2c react with CO to produce [Ir(CO)x(PPh3)2]+(from 1c) and [Ir(CO)y(PPh3)]+(from 2c) intercalated clays. Reactions of 1c and 2c with H2 produce cyclooctane and unknown iridium complexes remaining in the layers of the clay. While both the catalytic hydrogenation and isomerization (double-bond migration and cis–trans conversion) of olefins with 1 and 2 are in general retarded by intercalation of the catalysts, isomerization is relatively more suppressed than hydrogenation. Selective hydrogenation of the vinyl group of 4-vinylcyclohexene was found to be somewhat higher with 1c than with 1.

The complexes [Rh(CO)(PPh3)3]ClO41 and [Ir(cod)(PhCN)(PPh3)]ClO42(cod = cycloocta-1,5-diene), rapidly catalyse the double-bond migration of 2-ethylprop-2-en-1-ol 3 and prop-2-en-1-ol 4, respectively to generate a significant amount of the enols 2-methylbut-1-en-1-ol 5 and prop-1-en-1-ol 6 in the absence of a solvent and in CD3COCD3. Both enols 5 and 6 are quite stable and slowly undergo ketonization to the corresponding carbonyl compounds at room temperature in the absence of a solvent and in aprotic solvents. Detailed 1H NMR spectral data at 300 MHz suggest that two isomers (Z and E) of compound 5 are simultaneously produced in the reaction of 3 and 1, the ratio of the isomers (major:minor) being ca. 6–9 : 1. Reaction of compound 4 with 2 also generates the Z(major) and E isomers (minor product) of 6. The Z isomer initially generated rapidly undergoes isomerization to give the E isomer in the presence of 2, while both the Z and E isomers relatively slowly undergo ketonization. Additional 1H and 13C NMR and infrared spectral data for Me2CCHOD and Me2CDCHO are reported with some experimental details.

New cationic iridium(I) complexes, [Ir(cod)(PPh3)L]ClO41[cod = cycloocta-1,5-diene; L = PhCN, PhCHCHCN, CH2CHCN, CH2C(Me)CN, MeCHCHCN or CH2CHCH2CN co-ordinated through the nitrogen atom], have been prepared by the reactions of [IrCl(cod)(PPh3)] with AgClO4 in the presence of L. Reaction of [Ir(cod)(PPh3)(PhCN)]ClO41a with H2 gives the cis-dihydridoiridium(III) complex [IrH2(cod)(PPh3)(PhCN)]ClO42a where the two hydrides are trans to PhCN and an olefinic group of cod, respectively. Complex 2a is stable both in solution and in the solid state at low temperature and decomposes at 15 °C to give cyclooctane and unidentified Ir–cod complex(es). The nitrile (L) in 1 is readily replaced by both PPh3 and CO, while cod is replaced only by CO. In the presence of complexes 1, unsaturated alcohols such as CH2CHCH2OH, CH2CHCH(Me)OH and CH2CHCH(Ph)OH rapidly undergo isomerization to the corresponding saturated carbonyl compounds at room temperature. Complex 1a catalyses the hydrogenation of unsaturated aldehydes, PhCHCRCHO (R = H, Me or Cl) to give PhCHCRCH2OH, PhCH2CHRCHO and PhCH2CHRCH2OH under H2(pH2= 6 atm) at 50 °C.