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REACTION OF DIALKYLMAGNESIUM WITH CARBON MONOXIDE AND NITROSODURENE
Reaction between diethylmagnesium and carbon monoxide gives rise to the formation of pentanone-3, pentanol-3, 3-ethylpentanol-3, 3-ethyl-3-hydroxyhexanone-4 and 3-ethylhexanone-4.The use of CO and application of C NMR spectroscopy revealed that C2H5COCH(C2H5)2 arose after hydrolysis of C2H5COC(C2H5)2MgC2H5.Reaction between (C2H5)2Mg and nitrosodurene proceeds according to the nitrene-radical mechanism and the EPR spectrum presents a signal derived from Me4PhN(radical)-N(PhMe4)OMgC2H5.Upon this basis a carbene-radical mechanism is proposed for the reaction between carbon monoxide and diethylmagnesium.
Sobota, Piotr,Nowak, Marek,Kramarz, Wanda
p. 161 - 168
(1984)
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Selective Hydrogenation by Pd Nanoparticles Embedded in Polyelectrolyte Multilayers
Alternating adsorption of poly(acrylic acid) and a polyethylenimine?Pd(II) complex on alumina and subsequent reduction of Pd(II) by NaBH4 yield catalytic Pd nanoparticles embedded in multilayer polyelectrolyte films. The polyelectrolytes limit aggregation of the particles and impart catalytic selectivity in the hydrogenation of α-substituted unsaturated alcohols by restricting access to catalytic sites. Hydrogenation of allyl alcohol by encapsulated Pd(0) nanoparticles can occur as much as 24-fold faster than hydrogenation of 3-methyl-1-penten-3-ol. Additionally, the nanoparticle/polyelectrolyte system suppresses unwanted substrate isomerization, when compared to a commercial palladium catalyst. Selective diffusion through poly(acrylic acid)/polyethlyenimine membranes suggests that hydrogenation selectivities are due to different rates of diffusion to nanoparticle catalysts. First-order kinetics are also consistent with a diffusion-limited mechanism. Further exploitation of the versatility of polyelectrolyte films should increase selectivity in hydrogenation as well as other reactions. Copyright
Kidambi, Srividhya,Dai, Jinhua,Li, Jin,Bruening, Merlin L.
p. 2658 - 2659
(2004)
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Ambient Hydrogenation and Deuteration of Alkenes Using a Nanostructured Ni-Core–Shell Catalyst
A general protocol for the selective hydrogenation and deuteration of a variety of alkenes is presented. Key to success for these reactions is the use of a specific nickel-graphitic shell-based core–shell-structured catalyst, which is conveniently prepared by impregnation and subsequent calcination of nickel nitrate on carbon at 450 °C under argon. Applying this nanostructured catalyst, both terminal and internal alkenes, which are of industrial and commercial importance, were selectively hydrogenated and deuterated at ambient conditions (room temperature, using 1 bar hydrogen or 1 bar deuterium), giving access to the corresponding alkanes and deuterium-labeled alkanes in good to excellent yields. The synthetic utility and practicability of this Ni-based hydrogenation protocol is demonstrated by gram-scale reactions as well as efficient catalyst recycling experiments.
Beller, Matthias,Feng, Lu,Gao, Jie,Jackstell, Ralf,Jagadeesh, Rajenahally V.,Liu, Yuefeng,Ma, Rui
supporting information
p. 18591 - 18598
(2021/06/28)

Manganese-Catalyzed Hydrogenation of Ketones under Mild and Base-free Conditions
In this paper, several Mn(I) complexes were applied as catalysts for the homogeneous hydrogenation of ketones. The most active precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe) (CO)3(CH2CH2CH3)]. The reaction proceeds at room temperature under base-free conditions with a catalyst loading of 3 mol % and a hydrogen pressure of 10 bar. A temperature-dependent selectivity for the reduction of α,β-unsaturated carbonyls was observed. At room temperature, the carbonyl group was selectively hydrogenated, while the C=C bond stayed intact. At 60 °C, fully saturated systems were obtained. A plausible mechanism based on DFT calculations which involves an inner-sphere hydride transfer is proposed.
Brünig, Julian,Kirchner, Karl,Veiros, Luis F.,Weber, Stefan
supporting information
p. 1388 - 1394
(2021/05/31)

Uranyl(VI) Triflate as Catalyst for the Meerwein-Ponndorf-Verley Reaction
Catalytic transformation of oxygenated compounds is challenging in f-element chemistry due to the high oxophilicity of the f-block metals. We report here the first Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl substrates with uranium-based catalysts, in particular from a series of uranyl(VI) compounds where [UO2(OTf)2] (1) displays the greatest efficiency (OTf = trifluoromethanesulfonate). [UO2(OTf)2] reduces a series of aromatic and aliphatic aldehydes and ketones into their corresponding alcohols with moderate to excellent yields, using iPrOH as a solvent and a reductant. The reaction proceeds under mild conditions (80 °C) with an optimized catalytic charge of 2.3 mol % and KOiPr as a cocatalyst. The reduction of aldehydes (1-10 h) is faster than that of ketones (>15 h). NMR investigations clearly evidence the formation of hemiacetal intermediates with aldehydes, while they are not formed with ketones.
Kobylarski, Marie,Monsigny, Louis,Thuéry, Pierre,Berthet, Jean-Claude,Cantat, Thibault
supporting information
p. 16140 - 16148
(2021/11/01)

Hydrodeoxygenation of C4-C6 sugar alcohols to diols or mono-alcohols with the retention of the carbon chain over a silica-supported tungsten oxide-modified platinum catalyst
The hydrodeoxygenation of erythritol, xylitol, and sorbitol was investigated over a Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25, molar ratio) catalyst. 1,4-Butanediol can be selectively produced with 51% yield (carbon based) by erythritol hydrodeoxygenation at 413 K, based on the selectivity over this catalyst toward the regioselective removal of the C-O bond in the -O-C-CH2OH structure. Because the catalyst is also active in the hydrodeoxygenation of other polyols to some extent but much less active in that of mono-alcohols, at higher temperature (453 K), mono-alcohols can be produced from sugar alcohols. A good total yield (59%) of pentanols can be obtained from xylitol, which is mainly converted to C2 + C3 products in the literature hydrogenolysis systems. It can be applied to the hydrodeoxygenation of other sugar alcohols to mono-alcohols with high yields as well, such as erythritol to butanols (74%) and sorbitol to hexanols (59%) with very small amounts of C-C bond cleavage products. The active site is suggested to be the Pt-WOx interfacial site, which is supported by the reaction and characterization results (TEM and XAFS). WOx/SiO2 selectively catalyzed the dehydration of xylitol to 1,4-anhydroxylitol, whereas Pt-WOx/SiO2 promoted the transformation of xylitol to pentanols with 1,3,5-pentanetriol as the main intermediate. Pre-calcination of the reused catalyst at 573 K is important to prevent coke formation and to improve the reusability.
Betchaku, Mii,Cao, Ji,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi,Yabushita, Mizuho
supporting information
p. 5665 - 5679
(2021/08/16)

Chromium-Catalyzed Production of Diols From Olefins
Processes for converting an olefin reactant into a diol compound are disclosed, and these processes include the steps of contacting the olefin reactant and a supported chromium catalyst comprising chromium in a hexavalent oxidation state to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the diol compound. While being contacted, the olefin reactant and the supported chromium catalyst can be irradiated with a light beam at a wavelength in the UV-visible spectrum. Optionally, these processes can further comprise a step of calcining at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.
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(2021/03/19)

Synthesis and characterization of new ruthenium(III) complexes derived from fluoreneamine-based Schiff base ligands and their catalytic activity in transfer hydrogenation of ketones
An easy and convenient synthesis of a new series of octahedral ruthenium(III) complexes bearing Schiff base ligands of general formula [RuCl2(EPh3)2(L)] (where E = P, As and L = O,N-donor Schiff bases) has been reported. The composition of all complexes has been unequivocally characterized by spectral (IR, UV-vis, EPR) and ESI-MS techniques. The substituted Schiff base ligands behave as bidentate O,N-donors and coordinate to ruthenium via the phenolic oxygen, the azomethine nitrogen. Complexes 1–6 have been proven to catalyze the transfer hydrogenation of linear, cyclic and aromatic ketones to their corresponding secondary alcohols in the presence of i-PrOH/KOH at 80 °C with conversion up to 99%. The effect of other variables on the transfer hydrogenation reaction such as solvent, base, and catalyst loading is also reported.
Balasubramani, Kasturi,Nagalakshmi, Veerasamy,Nandhini, Raja,Venkatachalam, Galmari
(2020/03/16)

Mild-temperature hydrogenation of carbonyls over Co-ZIF-9 derived Co-ZIF-x nanoparticle catalyst
Benzimidazole and metal cobalt salts were employed in the synthesis of Co-ZIF-9 by solvothermal crystallization. Highly active catalysts for selective hydrogenation of carbonyl compounds were developed. The optimal nanocatalyst Co-ZIF-350 manifested remarkable activity and selectivity for the hydrogenation of cyclohexanone under mild conditions. Catalytic conversion of cyclohexanone reached the highest over the catalyst of Co-ZIF-9-pyrolyzed at 350 °C for 2 h, in which the conversion of cyclohexanone was 100 % and the selectivity of cyclohexanol was ＞99 % at 50 °C. A wide scope of ketones/aromatic aldehydes could be selectively reduced to the corresponding alcohols with high yields. Importantly, the nanocatalyst Co-ZIF-350 presented good tolerance of substrates with various functional groups under mild conditions.
Hu, Ao,Lu, Xinhuan,Pan, Haijun,Wang, Chenlong,Xia, Qinghua,Xia, Yongde,Yang, Lu,Yue, Fanfan,Zhang, Haifu,Zhou, Dan
(2020/08/21)

Chemoselective Electrochemical Hydrogenation of Ketones and Aldehydes with a Well-Defined Base-Metal Catalyst
Hydrogenation reactions are fundamental functional group transformations in chemical synthesis. Here, we introduce an electrochemical method for the hydrogenation of ketones and aldehydes by in situ formation of a Mn-H species. We utilise protons and electric current as surrogate for H2 and a base-metal complex to form selectively the alcohols. The method is chemoselective for the hydrogenation of C=O bonds over C=C bonds. Mechanistic studies revealed initial 3 e? reduction of the catalyst forming the steady state species [Mn2(H?1L)(CO)6]?. Subsequently, we assume protonation, reduction and internal proton shift forming the hydride species. Finally, the transfer of the hydride and a proton to the ketone yields the alcohol and the steady state species is regenerated via reduction. The interplay of two manganese centres and the internal proton relay represent the key features for ketone and aldehyde reduction as the respective mononuclear complex and the complex without the proton relay are barely active.
Fokin, Igor,Siewert, Inke
p. 14137 - 14143
(2020/10/12)

Methods and Compositions for Hydrodeoxygenation of Carbohydrates and Carbohydrate Analogs
This disclosure provides embodiments directed to compositions, methods, and processes to produce compounds having the structure: each of R1-R5 is selected from a hydroxyl group and hydrogen; and R1-R5 include at least one hydroxyl group and at least one hydrogen; and n=0-2. In particular, methods of the disclosure can include reacting a precursor, the precursor containing more oxygen (O) atoms than the compound, with a gas containing hydrogen (H2) in the presence of a catalyst.
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(2020/03/28)

Long-Range Self-Assembly of an Electron-Deficient Hexaazatrinaphthylene with Out-of-Plane Substituents
The unprecedented time-dependent long-range supramol-ecular assembly of electron-deficient hexaazatrinaphthylene (HATN) core based on peripheral crowding with three out-of-plane cyclic ketals is reported. The single-crystal X-ray structure of the diethyl derivative provided detailed information as to how four molecules in a repeating unit were packed in order to avoid steric crowding of the out-of-plane cyclic ketal side chain, providing locking and fastening for stabilizing the self-assembled structure. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) did not instantaneously show any phase transition upon the cooling process. To our surprise, POM images showed a nucleation of spherulite up to 100 μm after 24 hour later. X-ray diffraction data further confirmed that these soft crystal formed a hexagonal-like crystal. The long-range self-assembly of the new material showed a slight red shift in the UV-vis absorption spectra and further substantiated by computational method.
Chen, Yi-Ru,Zhang, Yong-Yun,Yeh, Ming-Che,Luo, Ying-Ting,Ong, Chi Wi
p. 613 - 618
(2019/12/24)

Rethinking Basic Concepts-Hydrogenation of Alkenes Catalyzed by Bench-Stable Alkyl Mn(I) Complexes
An efficient additive-free manganese-catalyzed hydrogenation of alkenes to alkanes with molecular hydrogen is described. This reaction is atom economic, implementing an inexpensive, earth-abundant nonprecious metal catalyst. The most efficient precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which undergoes rapid hydrogenolysis to form the active 16e Mn(I) hydride catalyst [Mn(dippe)(CO)2(H)]. A range of mono- A nd disubstituted alkenes were efficiently converted into alkanes in good to excellent yields. The hydrogenation of 1-alkenes and 1,1-disubstituted alkenes proceeds at 25 °C, while 1,2-disubstituted alkenes require a reaction temperature of 60 °C. In all cases, a catalyst loading of 2 mol % and a hydrogen pressure of 50 bar were applied. A mechanism based on DFT calculations is presented, which is supported by preliminary experimental studies.
Weber, Stefan,St?ger, Berthold,Veiros, Luis F.,Kirchner, Karl
p. 9715 - 9720
(2019/10/14)

Manganese(I)-Catalyzed Transfer Hydrogenation and Acceptorless Dehydrogenative Condensation: Promotional Influence of the Uncoordinated N-Heterocycle
The four bidentate manganese(I) complexes [(C5H4N-C5H3N-OH)Mn(CO)3Br] (1), [(C9H6N-C5H3N-OH)Mn(CO)3Br] (2), [(C8H5N2-C5H3N-OH)Mn(CO)3Br] (3), and [(C8H5N2-C5H3N-OCH3)Mn(CO)3Br] (4) were synthesized. These complexes were tested as catalysts for the transfer hydrogenation of ketones, and 3 showed the highest activity. The reactions proceeded well with 0.5 mol % of catalyst loading and 20 mol % of t-BuOK at 85 °C for 24 h. Furthermore, 3 was also used as a catalyst for the synthesis of primary alcohols via transfer hydrogenation of aldehydes and the synthesis of 1,2-disubstituted benzimidazoles and quinolines via acceptorless dehydrogenative condensations.
Zhang, Chong,Hu, Bowen,Chen, Dafa,Xia, Haiping
p. 3218 - 3226
(2019/09/13)

Mont-K10 Supported Fe(II) Schiff-Base Complex as an Efficient Catalyst for Hydrogenation of Ketones
Abstract: A new Fe(II) Schiff base complex anchored on mont-K10 (Fe@imine-mont-K10) was synthesized and extensively characterized by FTIR, powder X-ray diffraction, SEM–EDX, TEM, ESR, X-ray photoelectron spectroscopy (XPS), BET surface area measurement, solid state 29Si NMR and ICP-AES analysis. The catalytic activity of the complex was investigated for hydrogenation of ketones. The results indicated that it exhibited good catalytic activity for hydrogenation of aromatic as well as aliphatic ketones in i-PrOH/CH3CN (1:1) using Na-i-OPr as base at 80?°C resulting in moderate to excellent isolated yields (51–99%) of their corresponding products. The catalyst shows good reusability. Graphical Abstract: [Figure not available: see fulltext.].
Sultana, Samim,Borah, Geetika,Gogoi, Pradip. K.
p. 2142 - 2157
(2019/05/28)

Half?Sandwich (η6?p?Cymene) Ruthenium(II) complexes bearing 5?Amino?1?Methyl?3?Phenylpyrazole Schiff base ligands: Synthesis, structure and catalytic transfer hydrogenation of ketones
New (η6?p?cymene) ruthenium(II) complexes containing Schiff base ligands of the general composition [RuCl(η6?p?cymene)(L1?3)] have been synthesized. The complexes were characterized by analytical and spectral (FT?IR, UV–Vis, 1H NMR and 13C NMR) methods. The molecular structure of the representative complex [RuCl(η6?p?cymene)(L3)] 6 was determined by single crystal X?ray diffraction studies, revealing a pseudo-octahedral piano stool geometry around ruthenium(II) ion. Further, one of the complexes 6 was screened for their efficiency as a catalyst in the transfer hydrogenation of various ketones to alcohols in the presence of KOH and 2?propanol showed an excellent conversion up to 99%. Under the optimized conditions, the influence of base, reaction temperature and substrate scope was also reported.
Ramesh, Madhan,Venkatachalam, Galmari
p. 47 - 55
(2018/11/10)

Structural basis for a highly (S)-enantioselective reductase towards aliphatic ketones with only one carbon difference between side chain
Aliphatic ketones, such as 2-butanone and 3-hexanone, with only one carbon difference among side chains adjacent to the carbonyl carbon are difficult to be reduced enantioselectively. In this study, we utilized an acetophenone reductase from Geotrichum candidum NBRC 4597 (GcAPRD) to reduce challenging aliphatic ketones such as 2-butanone (methyl ethyl ketone) and 3-hexanone (ethyl propyl ketone) to their corresponding (S)-alcohols with 94% ee and > 99% ee, respectively. Through crystallographic structure determination, it was suggested that residue Trp288 limit the size of the small binding pocket. Docking simulations imply that Trp288 plays an important role to form a C-H?π interaction for proper orientation of ketones in the pro-S binding pose in order to produce (S)-alcohols. The excellent (S)-enantioselectivity is due to a non-productive pro-R binding pose, consistent with the observation that the (R)-alcohol acts as an inhibitor of (S)-alcohol oxidation.
Koesoema, Afifa Ayu,Sugiyama, Yosuke,Xu, Zichang,Standley, Daron M.,Senda, Miki,Senda, Toshiya,Matsuda, Tomoko
p. 9543 - 9553
(2019/09/16)

Highly Efficient Abnormal NHC Ruthenium Catalyst for Oppenauer-Type Oxidation and Transfer Hydrogenation Reactions
The ruthenium complex [Ru(OAc)(a-PC)2]Br (3) containing two abnormal NHC ligands is obtained by reaction of Ru(OAc)2(PPh3)2 (1) with 1-(2-diphenylphosphinoethyl)-3-mesitylimidazolium bromide in the presence of NaOAc. Complex 3 catalyzes the Oppenauer-type oxidation of a number of alcohols at unrivalled reaction rates reaching TOFs up to 550 000 h-1, at low catalyst loadings (S/C higher than 10 000) and using acetone in stoichiometric amounts. Complex 3 is also highly active in the reverse transfer hydrogenation of several ketones with 2-propanol, displaying TOFs up to 600 000 h-1
Pardatscher, Lorenz,Hofmann, Benjamin J.,Fischer, Pauline J.,H?lzl, Sebastian M.,Reich, Robert M.,Kühn, Fritz E.,Baratta, Walter
p. 11302 - 11306
(2019/11/21)

A porous metal-organic aerogel based on dirhodium paddle-wheels as an efficient and stable heterogeneous catalyst towards the reduction reaction of aldehydes and ketones
A new metal-organic aerogel (MOA-Rh-2) containing dirhodium paddle-wheels has been prepared from the reaction of dirhodium(ii) tetracarboxylate (Rh2(OAc)4) and tetrakis(4-carboxyphenyl)porphyrin (TCPP) in a mixed solvent of DMF and water, followed by supercritical CO2 extraction. MOA-Rh-2 has been fully characterized by ICP-OES, EDS, XPS, PXRD, SEM, TEM and TGA. Its porosity has been confirmed by N2 adsorption isotherms at 77 K, and the Barrett-Joyner-Halenda pore size is centered at 3.5 nm. The existence of mesopores has been further verified by dye adsorption tests using methylene blue (14.4 × 6.1 ?2) and rhodamine B (15.8 × 11.8 × 6.8 ?3). MOA-Rh-2 is air and moisture-stable. The catalytic results show that, under an air atmosphere and at ambient temperature, a low loading (0.1-0.4 mol%) of MOA-Rh-2 can efficiently promote the hydrosilylation of aldehydes and ketones with the commercially available silane of PhSiH3. After catalytic reactions, MOA-Rh-2 can be recycled and reused for 5 runs without significant loss of the activity, and the reaction conversions are in the range of 89-99%.
Liu, Gang,Wang, Yanhu,Zhu, Baofu,Zhang, Li,Su, Cheng-Yong
p. 11358 - 11363
(2018/07/24)

Insights into the role of nanoalloy surface compositions toward catalytic acetone hydrogenation
A significant composition-dependent catalysis behavior was observed in catalytic acetone hydrogenation. Carbon supported PtRu alloy nanoparticles (NPs) with optimal surface composition achieved ultra-efficient and highly selective production of isopropyl alcohol.
Yang, Zhao,Zhu, Huaze,Zhu, Huijuan,Wang, Yanbing,Che, Liming,Yang, Zhiqing,Fang, Jun,Wu, Qi-Hui,Chen, Bing Hui
supporting information
p. 8351 - 8354
(2018/08/04)

An air and moisture tolerant iminotrihydroquinoline-ruthenium(ii) catalyst for the transfer hydrogenation of ketones
Reaction of 8-amino-5,6,7,8-tetrahydroquinoline with RuCl2(PPh3)3 at room temperature affords the ruthenium(ii) chelate (8-NH2-C9H10N)RuCl2(PPh3)2 (E), in which the two triphenylphosphine ligands are disposed mutually cis. By contrast, when the reaction is performed at reflux ligand oxidation/dehydrogenation occurs along with cis-trans reorganization of the triphenylphosphines to form the 8-imino-5,6,7-trihydroquinoline-ruthenium(ii) complex, (8-NH-C9H9N)RuCl2(PPh3)2 (F). Complex F can also be obtained in higher yield by heating a solution of E alone to reflux. Comparison of their molecular structures highlights the superior binding properties of the bidentate imine ligand in F over its amine-containing counterpart in E. Both complexes are highly effective in the transfer hydrogenation of a wide range of alkyl-, aryl- and cycloalkyl-containing ketones affording their corresponding secondary alcohols with loadings of as low as 0.1 mol%. Significantly, F can deliver excellent conversions even in bench quality 2-propanol in reaction vessels open to the air, whereas the catalytic efficiency of E is diminished by the presence of air but only operates efficiently under inert conditions.
Li, Jiaoyan,Ma, Yingmiao,Wang, Zheng,Liu, Qingbin,Solan, Gregory A.,Ma, Yanping,Sun, Wen-Hua
p. 8738 - 8745
(2018/07/13)

Application of Ni(II) complexes of air stable Schiff base functionalized N-heterocyclic carbene ligands as catalysts for the transfer hydrogenation of aliphatic ketones
New air stable N-heterocyclic carbene functionalized Schiff base ligands (L) of the type 2-[-2-[3-(R)imidazol-1-yl]ethyliminomethyl]phenol [R = methyl (2), 2-pyridylmethyl (3)] were synthesized and characterized by NMR, IR, MS, and CHN analysis. Single crystal X-ray structural analysis of their Ni(II) complexes revealed square planar arrangement of the chelating ligands coordinated in tridentate (2, C^N^O) and tetradentate (3, N^C^N^O) modes around the metal. The three new isolated and fully characterized complexes were utilized as catalysts for the catalytic transfer hydrogenation of aliphatic ketones in 2-propanol as solvent and source of hydrogen. Based on 0.2 mol% catalyst concentration, the complexes showed activity for aliphatic ketones and 100% conversion (turnover number of 500) for cyclohexanone and all the aromatic ketones tested.
Abubakar, Samaila,Bala, Muhammad D.
p. 2913 - 2923
(2018/09/27)

Interplay between H-bonding and interpenetration in an aqueous copper(ii)-aminoalcohol-pyromellitic acid system: self-assembly synthesis, structural features and catalysis
Two new copper(ii) coordination compounds, [Cu(H1.5mdea)2]2(H2pma) (1a) and [{Cu2(μ-Hmdea)2}2(μ4-pma)]n·2nH2O (1b), were self-assembled at different temperatures from the same multicomponent reaction system, comprising copper(ii) nitrate, N-methyldiethanolamine (H2mdea), pyromellitic acid (H4pma), and potassium hydroxide. Products 1a and 1b were isolated as microcrystalline solids and fully characterized and their structures were established by single-crystal X-ray diffraction. Compound 1a features the bis-aminoalcohol(ate) monocopper(ii) units and H2pma2? anions that are multiply interconnected by strong H-bonds into a firm 2D H-bonded layer. Compound 1b reveals the bis-aminoalcoholate dicopper(ii) motifs that are interlinked by the μ4-pma4? spacers into a 3D + 3D interpenetrated metal-organic framework. From a topological perspective, both networks of 1a and 1b are uninodal and driven by similar 4-connected H2pma2? or pma4? nodes, but result in distinct sql and dia topologies, respectively. Compound 1a was applied as an efficient catalyst for two model cycloalkane functionalization reactions: (1) oxidation by H2O2 to form cyclic alcohols and ketones and (2) hydrocarboxylation by CO/H2O and S2O82? to form cycloalkanecarboxylic acids. The substrate scope, effects of various reaction parameters, selectivity and mechanistic features were also investigated.
Fernandes, Tiago A.,Kirillova, Marina V.,André, Vania,Kirillov, Alexander M.
p. 16674 - 16683
(2018/12/05)

Iridium Clusters Encapsulated in Carbon Nanospheres as Nanocatalysts for Methylation of (Bio)Alcohols
C?H methylation is an attractive chemical transformation for C?C bonds construction in organic chemistry, yet efficient methylation of readily available (bio)alcohols in water using methanol as sustainable C1 feedstock is limited. Herein, iridium nanocatalysts encapsulated in yolk–shell-structured mesoporous carbon nanospheres (Ir@YSMCNs) were synthesized for this transformation. Monodispersed Ir clusters (ca. 1.0 nm) were encapsulated in situ and spatially isolated within YSMCNs by a silica-assisted sol–gel emulsion strategy. A selection of (bio)alcohols (19 examples) was selectively methylated in aqueous phase with good-to-high yields over the developed Ir@YSMCNs. The improved catalytic efficiencies in terms of activity and selectivity together with the good stability and recyclability were contributable to the ultrasmall Ir clusters with oxidation chemical state as a consequence of the confinement effect of YSMCNs with interconnected nanostructures.
Liu, Qiang,Xu, Guoqiang,Wang, Zhendong,Liu, Xiaoran,Wang, Xicheng,Dong, Linlin,Mu, Xindong,Liu, Huizhou
p. 4748 - 4755
(2017/12/15)

Half-Sandwich Osmium(II) Complexes with Bidentate N,N-Chelating Ligands and Their Use in the Transfer Hydrogenation of Ketones
The reaction of appropriate N,N-bidentate ligands with the [(η6-p-cymene)Os(μ-Cl)Cl]2dimer (p-cymene = C10H14), followed by metathesis reaction with NH4PF6, gave the new osmium(II) arene complex salts [(η6-p-cymene)OsCl(C5H4N-2-CH=N–R)]PF6, where [R = tert-butyl (1), isopropyl (2), 2,6-dimethylphenyl (3), or 2,6-diisopropylphenyl (4)]. The dimer was also reacted with the N,N′-bidentate ligands di-(2-pyridyl)amine (5), 4-phenyl-3,6-di(2-pyridyl)pyridazine (6), 4,4′-di-tert-butyl-2, 2′-bipyridine (7), and 5,5′-dimethyl-2,2′-bipyridine (8). In addition, the reaction of the precursor [(η6-C6H6)Os(μ-Cl)Cl]2with the N,N′-bidentate ligands gave [(η6-C6H6)OsCl(N,N)]2where N,N = 4,4′-di-tert-butyl-2,2′-bipyridine (9), 5,5′-dimethyl-2,2′-bipyridine (10), 3,6-bis(2-pyridyl)-4-phenyl pyridazine (11), or di-(2-pyridyl)amine (12). The compounds were characterized by using1H and13C NMR, UV/Vis, FTIR spectroscopy and elemental analysis. The single-crystal X-ray structures for compounds 1, 4, 8, 10, 11, and 12 showed that the osmium(II) complexes adopted the classical three-legged piano stool geometry. These osmium(II) compounds were found to be effective catalysts for the transfer hydrogenation of ketones into alcohols with NaOH as base and 2-propanol as the solvent and hydrogen source. A range of cyclic, aromatic, and aliphatic ketones was studied and good turnover numbers achieved.
Gichumbi, Joel M.,Omondi, Bernard,Friedrich, Holger B.
p. 915 - 924
(2017/02/15)

Orientation towards asymmetric transfer hydrogenation of ketones catalyzed by (pyrazolyl)ethyl)pyridine Fe(II) and Ni(II) complexes
Compounds 2-[1-(3,5-dimethylpyrazol-1-yl)ethyl]pyridine (L1) and 2-[1-(3,5-diphenylpyrazol-1-yl)ethyl]pyridine (L2) were obtained in a three-step procedure which involved the reduction of acetylpyridine using NaBH4, chlorination of the alcohol intermediate using SOCl2 and subsequent reaction with appropriate pyrazoles. Reactions of L1 and L2 with Ni(II) and Fe(II) halides produced the respective complexes Ni(L1)Br2 (1), Ni(L1)Cl2 (2), Fe(L1)Cl2 (3) and Ni(L2)Br2 (4) as racemic mixtures in moderate yields. The molecular structures of complexes 1 and 4 are dinuclear and mononuclear respectively. All the complexes (1–4) formed active catalysts for the transfer hydrogenation of ketones (THK) in 2-propanol at 82?°C affording conversions of 58%–84% within 48?h. The influence of catalyst structure, reaction conditions and identity of ketone substrates in the TH reactions have been successfully established.
Magubane, Makhosazane N.,Alam, Mohd Gulfam,Ojwach, Stephen O.,Munro, Orde Q.
p. 197 - 201
(2017/02/18)

Transfer hydrogenation of ketones catalysed by half-sandwich (η6-p-cymene) ruthenium(II) complexes incorporating benzoylhydrazone ligands
Neutral half-sandwich η6-p-cymene ruthenium(II) complexes of general formula [Ru(η6-p-cymene)Cl(L)] (HL?=?monobasic O, N bidendate benzoylhydrazone ligand) have been synthesized from the reaction of [Ru(η6-p-cymene)(μ-Cl)Cl]2 with acetophenone benzoylhydrazone ligands. All the complexes have been characterized using analytical and spectroscopic (Fourier transform infrared, UV–visible, 1H NMR, 13C NMR) techniques. The molecular structures of three of the complexes have been determined using single-crystal X-ray diffraction, indicating a pseudo-octahedral geometry around the ruthenium(II) ion. All the ruthenium(II) arene complexes were explored as catalysts for transfer hydrogenation of a wide range of aromatic, cyclic and aliphatic ketones with 2-propanol using 0.1?mol% catalyst loading, and conversions of up to 100% were obtained. Further, the influence of other variables on the transfer hydrogenation reaction, such as base, temperature, catalyst loading and substrate scope, was also investigated.
Mohan, Nanjan,Ramesh, Rengan
(2017/06/21)

New preparation method of 2-ethylbutyric acid
The invention provides a new preparation method of 2-ethylbutyric acid. The preparation method includes the steps of: performing a reaction to propyl aldehyde and ethyl magnesium halide to prepare 3-pentanol; preparing 3-halogenated pentane from the 3-pentanol; preparing a Grignard reagent from the 3-halogenated pentane, and performing a reaction with CO2 to prepare the 2-ethylbutyric acid. The synthesis route is represented as follows. The method employs easy-to-obtained raw materials and is high in atom economy and low in industrial cost, thereby avoiding some defects in conventional methods.
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(2017/07/21)

Influence of the functional groups of multiwalled carbon nanotubes on performance of Ru catalysts in sorbitol hydrogenolysis to glycols
Different functional groups (i.e. [sbnd]NH2, [sbnd]COOH, [sbnd]OH and nitrogen-doping) modified CNTs (denoted as AMCN, CMCN, HMCN and NMCN, respectively) supported ruthenium catalysts (Ru/AMCN, Ru/CMCN, Ru/HMCN and Ru/NMCN) were prepared by incipient wetness impregnation method. They were fully characterized by XRD, TG, Raman, XPS, TPD and TEM to elucidate the relationship between the physical property and their catalytic performance. TEM results shown that Ru particles were well dispersed on the surface for all the samples with the size of 1.48–1.99 nm. The effects of functional groups of carbon nanotubes (CNTs), nitrogen doping and base additive types on activity and selectivity of ethylene glycol (EG) and propylene glycol (1,2-PD) were investigated. In addition, the activity and final products distribution were much influenced by the properties of functional groups on CNTs and the type of metal cation of the base promoters, which probably participated in the reaction for accelerating a retro-aldol reaction for C[sbnd]C cleavage. Among the catalysts, Ru supported on AMCN exhibited the best catalytic activities and glycols selectivities than on MCN, CMCN, HMCN and NMCN.
Guo, Xingcui,Dong, Huihuan,Li, Bin,Dong, Linlin,Mu, Xindong,Chen, Xiufang
p. 79 - 87
(2016/12/09)

Synthesis and characterization of half-sandwich ruthenium(II) complexes with N-alkyl pyridyl-imine ligands and their application in transfer hydrogenation of ketones
A series of new arene ruthenium(II) complexes were prepared by reaction of ruthenium(II) precursors of the general formula [(η6-arene)Ru(μ-Cl)Cl]2 with N,N′-bidentate pyridyl-imine ligands to form complexes of the type [(η6-arene)RuCl(C5H4N-2-CH=N-R)]PF6, with arene?=?C6H6, R?=?iso-propyl (1a), tert-butyl (1b), cyclohexyl (1c), cyclopentyl (1d) and n-butyl (1e); arene?=?p-cymene, R?=?iso-propyl (2a), tert-butyl (2b). The complexes were fully characterized by 1H NMR and 13C NMR, UV–Vis and IR spectroscopies, elemental analyses, and the single-crystal X-ray structures of 2a and 2b have been determined. The single-crystal molecular structure revealed both compounds with a pseudo-octahedral geometry around the Ru(II) center, normally referred to as a piano stool conformation, with the pyridyl-imine as a bidentate N,N ligand. The activity of all complexes in the transfer hydrogenation of cyclohexanone in the presence of NaOH and iso-propanol is reported, the compounds showing turnover numbers of close to 1990 and high conversions. Complex 2b was also shown to be very effective for a range of aliphatic and cyclic ketones, giving conversions of up to 100?%.
Gichumbi, Joel M.,Friedrich, Holger B.,Omondi, Bernard
p. 867 - 877
(2016/10/25)

Ni Nanoparticles Stabilized by Poly(Ionic Liquids) as Chemoselective and Magnetically Recoverable Catalysts for Transfer Hydrogenation Reactions of Carbonyl Compounds
Imidazolium-based poly(ionic liquids) with hydroxide as the counter anion were employed to prepare stable aqueous dispersion of Ni nanoparticles. The synthesized poly(ionic liquid) stabilized Ni nanoparticles (PIL-Ni-NPs) were characterized by thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), powder XRD, TEM, Brunauer-Emmett-Teller (BET) surface area measurements, X-ray photoelectron spectroscopy (XPS), EPR, and UV/Vis spectroscopy. The PIL-Ni-NPs possess good catalytic activity towards transfer hydrogenation (TH) reactions of carbonyl compounds to their alcohol derivatives, in isopropanol at 80 °C in the absence of any additional base. This catalyst system chemoselectively reduces only the carbonyl group of α,β unsaturated carbonyl compounds. The magnetically separable PIL-Ni-NPs were recycled and reused for further TH reactions.
Vijayakrishna, Kari,Charan, K. T. Prabhu,Manojkumar, Kasina,Venkatesh, Sadhana,Pothanagandhi, Nellepalli,Sivaramakrishna, Akella,Mayuri, Pinapeddavari,Kumar, Annamalai Senthil,Sreedhar
p. 1139 - 1145
(2016/04/05)

Application of arene ruthenium(II) complexes with pyridine-2-carboxaldimine ligands in the transfer hydrogenation of ketones
The reaction of various pyridine-2-carboxaldimine ligands with the [(η6-arene)Ru(μ-Cl)Cl]2 dimer followed by a metathesis reaction with ammonium hexaflourophosphate, yielded the ruthenium(II) arene complex salts [(η6-arene)RuCl(C5H4[Formula presented]6; where (arene?=?C6H6 (1), p-cymene (2), Ar?=?3, 5-dimethyl phenyl (a), 2,3-dimethyl phenyl (b), 2,5-dimethyl phenyl (c), 3,4-dimethyl phenyl (d)). The compounds were characterized by elemental analysis, FT- IR, UV–vis and 1H and 13C NMR. Single crystal X-ray structures for compounds 1a, 1d and 2e were also determined and showed that the ruthenium(II) centre has a pseudo-octahedral geometry and the molecule adopted a three legged piano stool geometry in which the arene ring occupies the apex and the nitrogen atoms of the N,N′-bidentate ligand and the chloride atom the base of the stool. The Ru(II) complex salts were active for the catalytic transfer hydrogenation of ketones into alcohols in the presence of NaOH using 2-propanol as the hydrogen source at 82?°C. The complexes were suitable for a wide range of aliphatic, cyclic and aromatic ketones giving good turn over numbers.
Gichumbi, Joel M.,Friedrich, Holger B.,Omondi, Bernard
p. 29 - 38
(2016/07/14)

Structural, kinetic, and DFT studies of the transfer hydrogenation of ketones mediated by (pyrazole)pyridine iron(II) and nickel(II) complexes
A series of iron(ii) and nickel(ii) complexes chelated by 2-pyrazolyl(methyl)pyridine (L1), 2,6-bis(pyrazolylmethyl)pyridine (L2), and 2,6-bis(pyrazolyl)pyridine (L3) ligands have been investigated as transfer hydrogenation (TH) catalysts for a range of ketones. Nine chelates in total were studied: [Ni(L1)Br2] (1), [Ni(L1)Cl2] (2), [Fe(L1)Br2] (3), [Ni(L2)Br2] (4), [Ni(L2)Br2] (5), [Fe(L2)Cl2] (6), [Ni(L3)Br2] (7), [Ni(L3)Br2] (8), and [Fe(L3)Cl2] (9). Attempted crystallization of complexes 4 and 6 afforded stable six-coordinate cationic species 4a and 6a with a 2:1 ligand:metal (L:M) stoichiometry, as opposed to the monochelates that function as precursors to catalytic species for TH reactions. Crystallization of 7·4H2O and 8·2H2O, in contrast, afforded tri- and bis(aqua) salts of L3 chelated to Ni(ii) in a 1:1 L:M stoichiometry, respectively. Complexes 1-9 formed active catalysts for the TH of a range of ketones in 2-propanol at 82 °C. Both the nature of the metal ion and ligand moiety had a discernible impact on the catalytic activities of the complexes, with nickel(ii) chelate 5 affording the most active catalyst (kobs, 4.3 × 10-5 s-1) when the inductive phase lag was appropriately modelled in the kinetics. Iron(ii) complex 3 formed the most active TH catalyst without a significant inductive phase lag in the kinetics. DFT and solid angle calculations were used to rationalize the kinetic data: both steric shielding of the metal ion and electronic effects correlating with the metal-ligand distances appear to be significant factors underpinning the reactivity of 1-9. Catalysts derived from 1 and 9 exhibit a distinct preference for aryl ketone substrates, suggesting the possible involvement of π-type catalyst?substrate adducts in their catalytic cycles. A catalytic cycle involving only 4 steps (after induction) with stable DFT-simulated structures is proposed which accounts for the experimental data for the system.
Magubane, Makhosazane N.,Nyamato, George S.,Ojwach, Stephen O.,Munro, Orde Q.
p. 65205 - 65221
(2016/07/23)

Transfer hydrogenation reaction using novel ionic liquid based Rh(I) and Ir(III)-phosphinite complexes as catalyst
Hydrogen transfer reduction methods are attracting increasing interest from synthetic chemists in view of their operational simplicity. Thus, interaction of [Rh(μ-Cl)(cod)]2and Ir(η5-C5Me5)(μ-Cl)Cl]2with phosphinite ligand [(Ph2PO)-C7H11N2Cl]Cl, 1 gave new monodendate (1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-yl diphenylphosphinite chloride) (chloro ?4-1,5-cyclooctadiene rhodium(I))], 2 and (1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-yl diphenylphosphinite chloride) (dichloro ?5-pentamethylcyclopentadienyl iridium(III))], 3 complexes, which were characterized by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analysis.1H-{31P} NMR,1H-13C HETCOR or1H-1H COSY correlation experiments were used to confirm the spectral assignments. The novel catalysts were applied to transfer hydrogenation of acetophenone derivatives using 2-propanol as a hydrogen source. The results showed that the corresponding alcohols could be obtained with high activity (up to 99%) under mild conditions. Notably, (1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-yl diphenylphosphinite chloride) (chloro ?4-1,5-cyclooctadiene rhodium(I))], 2 complex is much more active than the other analogous complex, 3 in the transfer hydrogenation. Furthermore, compound, 2 acts as excellent catalysts, giving the corresponding alcohols in 97–99% conversions in 5?min (TOF?≤?1176?h?1).
Elma Karaka?, Duygu,Durap, Feyyaz,Baysal, Ak?n,Ocak, Yusuf Selim,Rafikova, Khadichakhan,Kaya, Eda ?avu?,Zazybin, Alexey,Temel, Hamdi,Kayan, Cezmi,Meri?, Nermin,Aydemir, Murat
p. 25 - 32
(2016/10/11)

METHOD FOR PRODUCING HEXANOL/PENTANOL
PROBLEM TO BE SOLVED: To provide a method for producing hexanol/pentanol, which, in the presence of a catalyst, enables hexanol and pentanol to be obtained efficiently from cellulose and hemicellulose in cellulosic biomass, respectively. SOLUTION: Hexanol and pentanol are obtained by hydrolyzing, saccharizing, and at the same time hydrocracking cellulosic biomass in an aqueous phase in the presence of an Ir-Re(iridium-rhenium)-based catalyst and at a temperature at which cellulose/hemicellulose are decomposed, and by dissolving hexanol/pentanol in an oil phase comprising a liquid hydrocarbon arranged in proximity. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2016,JPOandINPIT
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(2017/01/23)

Photooxygenation of alkanes by dioxygen with: P -benzoquinone derivatives with high quantum yields
Alkanes were oxygenated by dioxygen with p-benzoquinone derivatives such as p-xyloquinone in alkanes which are used as solvents to yield the corresponding alkyl hydroperoxides, alcohols and ketones under visible light irradiation with high quantum yields (Φ = 1000, 1600%). The photooxygenation is started by hydrogen atom abstraction from alkanes by the triplet excited states of p-benzoquinone derivatives as revealed by laser-induced transient absorption spectral measurements.
Ohkubo, Kei,Hirose, Kensaku,Fukuzumi, Shunichi
p. 731 - 734
(2016/07/06)

Solvent-Free Photooxidation of Alkanes by Dioxygen with 2,3-Dichloro-5,6-dicyano-p-benzoquinone via Photoinduced Electron Transfer
Photooxidation of alkanes by dioxygen occurred under visible light irradiation of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) which acts as a super photooxidant. Solvent-free hydroxylation of cyclohexane and alkanes is initiated by electron transfer from alkanes to the singlet and triplet excited states of DDQ to afford the corresponding radical cations and DDQ??, as revealed by femtosecond laser-induced transient absorption measurements. Alkane radical cations readily deprotonate to produce alkyl radicals, which react with dioxygen to afford alkylperoxyl radicals. Alkylperoxyl radicals abstract hydrogen atoms from alkanes to yield alkyl hydroperoxides, accompanied by regeneration of alkyl radicals to constitute the radical chain reactions, so called autoxidation. The radical chain is terminated in the bimolecular reactions of alkylperoxyl radicals to yield the corresponding alcohols and ketones. DDQ??, produced by the photoinduced electron transfer from alkanes to the excited state of DDQ, disproportionates with protons to yield DDQH2.
Ohkubo, Kei,Hirose, Kensaku,Fukuzumi, Shunichi
supporting information
p. 2255 - 2259
(2016/08/30)

16-Electron pentadienyl- and cyclopentadienyl-ruthenium half-sandwich complexes with bis(imidazol-2-imine) ligands and their use in catalytic transfer hydrogenation
Bis(η5-2,4-dimethylpentadienyl)ruthenium(ii), [(η5-C7H11)2Ru] (1, "open ruthenocene"), which has become accessible in high yield and large quantities via an isoprene-derived diallyl ruthenium(iv) complex, can be converted into the protonated open ruthenocene 2 by treatment with HBF4 and subsequently into the protonated half-open ruthenocene 3 by reaction with cyclopentadiene. The electronic structure of 3 was studied by DFT methods, revealing that the CH-agostic complex [(η5-C5H5)Ru{(1-4η)-C7H12-η2-C5,H5}]BF4 (A) represents the global minimum, which is 3.7 kcal mol-1 lower in energy than the hydride complex [(η5-C5H5)RuH(η5-C7H11)]BF4 (B). 2 and 3 were treated with the ligands N,N′-bis(1,3,4,5-tetramethylimidazolin-2-ylidene)-1,2-ethanediamine (BLMe) and N,N′-bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,2-ethanediamine (BLiPr) to afford the cationic 16-electron pentadienyl and cyclopentadienyl complexes [(η5-C7H11)Ru(BLR)]BF4 (4a, R = Me; 4b, R = iPr) and [(η5-C5H5)Ru(BLR)]BF4 (5a, R = Me; 5b, R = iPr). All complexes catalyse the transfer hydrogenation of acetophenone in isopropanol, and the most active complex 4a in this reaction was employed for the hydrogenation of a broader range of aliphatic and aromatic ketones.
Gl?ge, Thomas,Jess, Kristof,Bannenberg, Thomas,Jones, Peter G.,Langenscheidt-Dabringhausen, Nadine,Salzer, Albrecht,Tamm, Matthias
p. 11717 - 11724
(2015/06/30)

Chiral polyethers derived from BINOL and ECH as highly enantioselective and efficient catalysts for the borane reduction of prochiral ketones
Two novel polyethers derived from BINOL were synthesized and used to induce the enantioselective borane reduction of prochiral ketones. The polyethers gave the expected secondary alcohols with up to 98% yields and over 99% ee values. The recovered polyethers could be reused for many times to induce the enantioselective reduction of prochiral ketones without losing their enantioselective induction ability.
Zhang, An-Lin,Yu, Zeng-Da,Yang, Li-Wen,Yang, Nian-Fa,Peng, Dan
p. 407 - 412
(2015/01/30)

Understanding ketone hydrodeoxygenation for the production of fuels and feedstocks from biomass
Although we can efficiently convert bioderived furans into linear alkanes, the most energy-intensive step in this approach is the hydrodeoxygenation of the intermediate polyketone. To fully understand this process, we have examined the hydrodeoxygenation of a model compound, 3-pentanone, which allows us to follow this process stepwise using Pd/C, H2 (200 psi), and La(OTf)3 in acetic acid to remove the oxygen atom at temperatures between 25 and 200 C. We have found that ketone reduction to an alcohol is followed by acetoxylation, which provides a more facile route to C-O bond cleavage relative to the parent alcohol. (Chemical Presented).
King, Amanda E.,Brooks, Ty J.,Tian, Yong-Hui,Batista, Enrique R.,Sutton, Andrew D.
p. 1223 - 1226
(2015/02/19)

A ruthenium(II) bipyridine complex containing a 4,5-diazafluorene moiety: Synthesis, characterization and its applications in transfer hydrogenation of ketones and dye sensitized solar cells
The ruthenium(II) complex [Ru(bpy)2L](PF6)2, where bpy is 2,2′-bipyridine and L is 1,5-dihydro-2-H-cyclopenta[1,2-b:5,4-b′]dipyridine-2-one, was synthesized from the reaction of cis-Ru(bpy)2Cl2·2H2O with L, and isolated as the hexafluorophosphate salt. The structure of L was unequivocally elucidated by single-crystal X-ray diffraction analysis. The new ruthenium(II) complex was thoroughly characterized by 1H and 13C NMR spectroscopy, along with FTIR, UV-Vis and LC MS/MS Triple Quadrupole Mass spectroscopy and elemental analysis. The catalytic activity of [Ru(bpy)2L](PF6)2 was tested in the transfer hydrogenation of various ketones in 2-propanol as both the solvent and hydrogen donor. The usage of [Ru(bpy)2L](PF6)2 for the formation of a dye sensitized solar cell is also presented.
Baysal, Akin,Aydemir, Murat,Durap, Feyyaz,?zkar, Saim,Yildirim, Leyla Tatar,Ocak, Yusuf Selim
p. 55 - 61
(2015/02/19)

Solid-state molybdenum sulfide clusters with an octahedral metal framework as hydrogenation, dehydrogenation, and hydrogenolysis catalysts similar to the platinum group metals
Solid-state molybdenum sulfide clusters with a nonstoichiometric sulfur-deficient site, CuxMo6S8-δ (x = 2.94 and δ ? 0.3) and Mo6S8-δ (δ ? 0.4), catalyze the dehydrogenation of cyclohexene, the hydrogenation of alkyne, alkene, aldehyde, ketone, and nitrobenzene, and the hydrogenolysis of halogenobenzenes in a hydrogen stream above 300 °C. This catalytic behavior of the clusters is similar to that of the platinum group metals, which is attributable to the isoelectronicity of sulfur-coordinating molybdenum atom to the platinum group metals.
Kamiguchi, Satoshi,Arai, Kanako,Okumura, Kazu,Iida, Hajime,Nagashima, Sayoko,Chihara, Teiji
p. 417 - 421
(2015/10/28)

Polymer anchored ruthenium complex: A highly active and recyclable catalyst for one-pot azide-alkyne cycloaddition and transfer-hydrogenation of ketones under mild conditions
A new polymer supported Ru(III) complex has been synthesized and characterized. The catalytic performance of the complex has been tested for the first time azide-alkyne cycloaddition reaction in water and transfer-hydrogenation reaction of ketones in open air. 1,4-disubstituted-1,2,3-triazoles were obtained in excellent yields from azides and terminal alkynes in aqueous medium in the presence of the above catalyst. Aromatic ketones have been converted to their corresponding alcohols using the polymer supported Ru(III) catalyst. The effects of solvents, reaction time, catalyst amount for the azide-alkyne cycloaddition reaction and transfer-hydrogenation reaction were studied. This catalyst showed excellent catalytic activity and recyclability. The polymer supported Ru(III) catalyst could be easily recovered by filtration and reused more than five times without appreciable loss of its initial activity. There was no evidence of leached Ru from the catalyst during the course of reaction has been observed, suggesting true heterogeneity in the catalytic process.
Molla, Rostam Ali,Roy, Anupam Singha,Ghosh, Kajari,Salam, Noor,Iqubal, Md Asif,Tuhina,Islam, Sk Manirul
p. 170 - 179
(2015/01/08)

Catalytic Transfer Hydrogenation with a Methandiide-Based Carbene Complex: An Experimental and Computational Study
The transfer hydrogenation (TH) reaction of ketones with catalytic systems based on a methandiide-derived ruthenium carbene complex was investigated and optimised. The complex itself makes use of the noninnocent behaviour of the carbene ligand (M=CR2→MH-C(H)R2), but showed only moderate activity, thus requiring long reaction times to achieve sufficient conversion. DFT studies on the reaction mechanism revealed high reaction barriers for both the dehydrogenation of iPrOH and the hydrogen transfer. A considerable improvement of the catalytic activity could be achieved by employing triphenylphosphine as additive. Mechanistic studies on the role of PPh3 in the catalytic cycle revealed the formation of a cyclometalated complex upon phosphine coordination. This ruthenacycle was revealed to be the active species under the reaction conditions. The use of the isolated complex resulted in high catalytic activities in the TH of aromatic as well as aliphatic ketones. The complex was also found to be active under base-free conditions, suggesting that the cyclometalation is crucial for the enhanced activity.
Weismann, Julia,Gessner, Viktoria H.
supporting information
p. 16103 - 16112
(2015/11/03)

Hydrogenation of ketones over bifunctional Pt-heteropoly acid catalyst in the gas phase
Gas-phase hydrogenation of a wide range of ketones to alkanes, including hydrogenation of aliphatic ketones and acetophenone, was investigated using bifunctional metal-acid catalysis. The catalysts were comprised of a metal (Pt, Ru, Ni, and Cu) supported on acidic caesium salt of tungstophosphoric heteropoly acid Cs2.5H0.5PW12O40 (CsPW). The reaction occurred via a sequence of steps involving hydrogenation of ketone to alcohol on metal sites followed by dehydration of alcohol to alkene on acid sites and finally hydrogenation of alkene to alkane on metal sites. Catalyst activity decreased in the order: Pt > Ru >> Ni > Cu. Pt/CsPW showed the highest catalytic activity, giving almost 100% alkane yield at 100 °C and 1 bar pressure. Evidence is provided that the reaction with Pt/CsPW at 100 °C is limited by ketone-to-alcohol hydrogenation, whereas at lower temperatures (≤60 °C) by alcohol dehydration yielding alcohol as themain product. The catalyst comprised of a physical mixture of Pt/C + CsPW was found to be highly efficientas well, which indicates that the reaction is not limited by migration of intermediates between metal andacid sites in the bifunctional catalyst.
Alharbi,Kozhevnikova,Kozhevnikov
p. 457 - 462
(2015/10/05)

Hydrodeoxygenation of vicinal OH groups over heterogeneous rhenium catalyst promoted by palladium and ceria support
Heterogeneous ReOx-Pd/CeO2 catalyst showed excellent performance for simultaneous hydrodeoxygenation of vicinal OH groups. High yield (> 99%), turnover frequency (300 h-1), and turnover number (10 000) are achieved in the reaction of 1,4-anhydroerythritol to tetrahydrofuran. This catalyst can be applied to sugar alcohols, and mono-alcohols and diols are obtained in high yields (≥ 85%) from substrates with even and odd numbers of OH groups, respectively. The high catalytic performance of ReOx-Pd/CeO2 can be assigned to rhenium species with + 4 or + 5 valence state, and the formation of this species is promoted by H2/Pd and the ceria support.
Ota, Nobuhiko,Tamura, Masazumi,Nakagawa, Yoshinao,Okumura, Kazu,Tomishige, Keiichi
supporting information
p. 1897 - 1900
(2015/02/19)

Novel cyclohexyl-based aminophosphine ligands and use of their Ru(II) complexes in transfer hydrogenation of ketones
Two new aminophosphines - furfuryl-(N-dicyclohexylphosphino)amine, [Cy 2PNHCH2-C4H3O] (1) and thiophene-(N-dicyclohexylphosphino)amine, [Cy2PNHCH 2-C4H3S] (2) - were prepared by the reaction of chlorodicyclohexylphosphine with furfurylamine and thiophene-2-methylamine. Reaction of the aminophosphines with [Ru(η6-p-cymene)(μ-Cl)Cl] 2 or [Ru(η6-benzene)(μ-Cl)Cl]2 gave corresponding complexes [Ru(Cy2PNHCH2-C4H 3O)(η6-p-cymene)Cl2] (1a), [Ru(Cy 2PNHCH2-C4H3O)(η6- benzene)Cl2] (1b), [Ru(Cy2PNHCH2-C 4H3S)(η6-p-cymene)Cl2] (2a) and [Ru(Cy2PNHCH2-C4H3S) (η6-benzene)Cl2] (2b), respectively, which are suitable catalyst precursors for the transfer hydrogenation of ketones. In particular, [Ru(Cy2PNHCH2-C4H 3S)(η6-benzene)Cl2] acts as a good catalyst, giving the corresponding alcohols in 98-99% yield in 30 min at 82 °C (up to time of flight ≤ 588 h-1).
Kayan, Cezmi,Meric, Nermin,Aydemir, Murat,Ocak, Yusuf Selim,Temel, Hamdi
p. 127 - 133
(2014/02/14)

Application of three-legged piano-stool cyclopentadienyl-N-heterocyclic carbene iron(II) complexes as in situ catalysts for the transfer hydrogenation of ketones
A one pot system has been developed based on nine related 1,3-dialkylated imidazolium salts for the in situ generation of N-heterocyclic carbene iron(II) complexes in which the complexes were directly tested as catalysts for the transfer hydrogenation of ketones. This is a simplified reproducible process that aims to eliminate unnecessary purification steps for the isolation of such catalysts prior to application. Complexes 10-12 have been prepared under similar conditions, isolated and structurally characterized by spectroscopic and crystallographic methods. Solid state structures of the three complexes were similar and showed distorted octahedral three-legged piano stool geometry around each iron center similar to reported complexes bearing related ligands. As a basis for comparison with the in situ catalyzed systems, the isolated complexes were also tested as catalysts for the transfer hydrogenation of ketones. As a result, under optimized reaction conditions, all the in situ generated catalysts were found to provide excellent activities similar to those based on the isolated complexes with moderate to excellent conversions to the desired alcohol products. Turn over numbers up to 200 at a conversion of 100% was recorded for a wide range of aliphatic, aromatic and cyclic ketones.
Bala, Muhammad D.,Ikhile, Monisola I.
p. 98 - 105
(2014/03/21)

Transfer hydrogenation of ketones catalyzed by new rhodium and iridium complexes of aminophosphine containing cyclohexyl moiety and photosensing behaviors of rhodium and iridium based devices
The reaction of [Rh(μ-Cl)(cod)]2 and Ir(η5- C5Me5)(μ-Cl)Cl]2 with aminophosphine ligands Cy2PNHCH2-C4H3X (X: O; S) gave a range of new monodendate [Rh(Cy2PNHCH2-C4H 3O)(cod)Cl], (1), [Rh(Cy2PNHCH2-C 4H3S)(cod)Cl], (2), [Ir(Cy2PNHCH 2-C4H3O)(η5-C5Me 5)Cl2], (3) and [Ir(Cy2PNHCH2-C 4H3S)(η5-C5Me 5)Cl2], (4) complexes, which were characterized by analytical and spectroscopic methods. The new rhodium(I) and iridium(III) catalysts were applied to transfer hydrogenation of acetophenone derivatives using 2-propanol as a hydrogen source. The results showed that the corresponding alcohols could be obtained with high activity (up to 99%) under mild conditions. Notably, [Rh(Cy2PNHCH2-C4H 3O)(cod)Cl] complex (1) is much more active than the other analogous complexes in the transfer hydrogenation. Moreover, organic-inorganic rectifying contacts were fabricated forming rhodium(I) and iridium(III) complex thin films on n-Si semiconductors and evaporating Au metal on the structures. Electrical properties of the contacts including ideality factor, barrier height and series resistance were determined using their current-voltage (I-V) data. The photoelectrical characteristics of the devices were examined under the light with 40-100 mW/cm2 illumination conditions. It was seen that light had strong effects on I-V characteristics of the devices and the ones fabricated using 3 and 4 complexes had unusually forward and reverse bias photoconducting behavior.
Rafikova, Khadichakhan,Kystaubayeva, Nurzhamal,Aydemir, Murat,Kayan, Cezmi,Ocak, Yusuf Selim,Temel, Hamdi,Zazybin, Alexey,Gürbüz, Nevin,?zdemir, Ismail
p. 1 - 8
(2014/03/21)

Ionic liquid based Ru(II)-phosphinite compounds and their catalytic use in transfer hydrogenation: X-ray structure of an ionic compound 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol
The compound 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride (1) was prepared from the reaction of 1-methylimidazole with epichlorohydrine. The corresponding phosphinite ligands were synthesized by the reaction 1-chloro-3-(3-methylimidazolidin-1-yl)propan-2-ol chloride, [C7H 15N2OCl]Cl with one equivalent of chlorodiphenylphosphine or chlorodicyclohexylphosphine, in anhydrous CH2Cl2 and under an inert argon atmosphere. [Ru(η6-arene)(μ-Cl)Cl] 2 dimers readily react with the phosphinite ligands [(Ph 2PO)-C7H14N2Cl]Cl (2) or [(Cy 2PO)-C7H14N2Cl]Cl (3) at room temperature to afford the cationic derivatives [Ru((Ph2PO)-C 7H14N2Cl)(η6-arene)Cl 2]Cl and [Ru((Cy2PO)-C7H14N 2Cl)(η6-arene)Cl2]Cl {arene: benzene (4), (5); p-cymene (6), (7)}. The structures of these ligands and their corresponding complexes have been elucidated by a combination of multinuclear NMR and IR spectroscopy, TGA/DTA and elemental analysis. The molecular structure of the ionic compound 1 was also determined by an X-ray single crystal diffraction study. Furthermore, the catalytic activity of complexes 4-7 for the transfer hydrogenation of various ketones was investigated and these complexes were found to be efficient catalysts in the transfer hydrogenation of various ketones, with excellent conversions up to 99%. Specifically, [Ru((Cy2PO)- C7H14N2Cl)(η6-benzene)Cl 2]Cl (5) and [Ru((Cy2PO)-C7H14N 2Cl)(η6-p-cymene)Cl2]Cl (7) act as excellent catalysts, giving the corresponding alcohols in 98-99% conversions in 5 min (TOF ≤ 1188 h-1).
Aydemir, Murat,Rafikova, Khadichakhan,Kystaubayeva, Nurzhamal,Pa?a, Salih,Meri?, Nermin,Ocak, Yusuf Selim,Zazybin, Alexey,Temel, Hamdi,Gürbüz, Nevin,?zdemir, Ismail
p. 245 - 255
(2014/07/21)

The application of tunable tridendate P-based ligands for the Ru(II)-catalysed transfer hydrogenation of various ketones
Two novel versatile tridendate aminophosphine-phosphinite and phosphinite ligands were prepared and their trinuclear neutral ruthenium(II) dichloro complexes were found to be effective catalysts for the transfer hydrogenation of various ketones in excellent conversions up to 99% in the presence of 2-propanol/NaOH in 0.1M isopropanol solution. Particularly, [Ru3 (PPh2OC2H4)2N-PPh2 (η6-p-cymene)3Cl6] acts as an excellent catalyst giving the corresponding alcohols in excellent conversion up to 99% (turnover frequency ≤ 1176 h-1). A comparison of the catalytic properties of the complexes is also discussed briefly. Furthermore, the structures of these ligands and their corresponding complexes have also been clarified using a combination of multinuclear NMR spectroscopy, infrared spectroscopy and elemental analysis. 1H-13C HETCOR or 1H-1H COSY correlation experiments were used to confirm the spectral assignments.
Meri, Nermin,Durap, Feyyaz,Aydemir, Murat,Baysal, Akn
p. 803 - 808
(2015/02/02)

The application of tunable tridendate P-based ligands for the Ru(II)-catalysed transfer hydrogenation of various ketones
Two novel versatile tridendate aminophosphine-phosphinite and phosphinite ligands were prepared and their trinuclear neutral ruthenium(II) dichloro complexes were found to be effective catalysts for the transfer hydrogenation of various ketones in excellent conversions up to 99% in the presence of 2-propanol/NaOH in 0.1M isopropanol solution. Particularly, [Ru3 (PPh2OC2H4)2 N-PPh2(η6-p-cymene)3Cl6] acts as an excellent catalyst giving the corresponding alcohols in excellent conversion up to 99% (turnover frequency ≤ 1176 h-1). A comparison of the catalytic properties of the complexes is also discussed briefly. Furthermore, the structures of these ligands and their corresponding complexes have also been clarified using a combination of multinuclear NMR spectroscopy, infrared spectroscopy and elemental analysis. 1H-13C HETCOR or 1H-1H COSY correlation experiments were used to confirm the spectral assignments.
Meric, Nermin,Durap, Feyyaz,Aydemir, Murat,Baysal, Akin
p. 803 - 808
(2015/02/19)