Arzumanyan, Ashot V

Tereshchenko A.A., Goncharova I.K., Zagrebaev A.D., Chapek S.V., Nechitailova I.O., Yu. Molodtsov D., Soldatov A.V., Beletskaya I.P., Arzumanyan A.V., Guda A.A.

Goncharova I., Kholodkov D., Beletskaya I., Arzumanyan A.

This study introduces the development of highly efficient and simple recyclable catalysts for hydrosilylation using polyols as a medium for heterophase catalytic systems. The system consists of a commercially available platinum precatalyst – K2PtCl4, and a surplus green solvent – glycerol (Gly), which can be easily prepared by dissolving K2PtCl4 in Gly at r.t. under air. The method allows for at least 60 cycles with a quantitative yield of the anti-Markovnikov product in air at r.t.; the product can be isolated from the catalytic system by simple decantation. The reaction proceeds at a high rate (from 10 min per cycle) even with small catalyst loadings (0.001-0.1 mol% Pt).

Goncharova I., Arzumanyan A.

This study presents a solution to the key challenge in modern chemistry of silicones – a functionalization of organosilicon compounds. We have previously shown the potential of the aerobic oxidation for a functionalization of several model p-tolyl-siloxanes to corresponding p-carboxyphenyl-derivatives. Unfortunately, this method has several drawbacks: limited scope, time and energy consumption, as well as scaling problems. We now present their solution. Mild and highly effective liquid-phase [M]-/organo-catalyzed aerobic functionalization of alkylaryl-siloxanes was developed. Reactions proceed at room temperature and atmospheric pressure within 0.5-24 h yielding products in quantitative conversions and high yields. Components of the catalytic system are simple, cheap and commercially available: Co(OAc)2 as earth-abundant metal-catalyst, and N-hydroxyphthalimide (NHPI) as an organo-catalyst. A unique combination of solvents with hexafluoroisopropanol (HFIP) being both co-solvent and process activator (usually in small quantities, 10-25%), provided high efficiency. HFIP allows to overcome scope limitations (most substrates were not oxidized in the absence of HFIP). It also dramatically increases process efficiency minimizing time and energy consumption (reaction time is 0.5-24 h, at r.t. and 1 atm) and solving scalability problems (≥100 g). Method allows to obtain a wide range of both carboxy-, carbonyl- and hydroxy-aryl-containing silanes/siloxanes of linear, hyperbranched, cyclic and cage (polyhedral oligomeric silsesquioxanes or spherosilicates) structure. This approach is applicable to both monomeric and oligomeric and polymeric substrates with various number of functional groups.

Goncharova I.K., Beletskaya I.P., Arzumanyan A.

AbstractThis concept addresses the main economic, environmental, scientific and technological issues associated with the use of homogeneous Pt‐catalysts in the important industrial hydrosilylation process. The development of biphase catalysis is proposed as the most promising approach. One solution we suggest is the use of ethylene glycol (EG) as a medium in biphase catalysis. We have previously shown that EG in Pt‐catalyzed hydrosilylation serves not only as a medium but also as a mild reducing agent of Pt‐ions to Pt0, as well as an effective ligand for the preparation of mononuclear Pt01‐complexes. These zero valent platinum complexes are single‐atom catalysts (SAC) and have high activity in hydrosilylation, stability during storage and the ability to be recycled multiple times (~40 times). This option of using an atomic catalyst allows us to combine the advantages of homogeneous and heterogeneous catalysts.

Goncharova I.K., Filatov S.A., Drozdov A.P., Tereshchenko A.A., Knyazev P.A., Guda A.A., Beletskaya I.P., Arzumanyan A.V.

This study presents a highly efficient and mild method for radical hydrosilylation of alkenes. The reaction proceeds under white-light, in the presence of Mn2(CO)10 pre-catalyst and HFIP as an additive, at r.t. and under air. Under white-light, [Mn]• is generated, which activates the Si–H-group to form Si• and trigger the autocatalytic process. HFIP acts as a unique activator which enables synthesis of the products with yields close to quantitative and with anti-Markovnikov selectivity. The method is applicable to terminal alkenes, including those with O-, N- and halogen-containing functional groups, styrene and allylbenzene derivatives, etc., as well as to a wide range of alkyl-, phenyl-, siloxy- and alkoxy-containing tertiary hydrosilanes. These conditions turned out to be most efficient for hydrosilylation of gaseous reagents such as ethylene and acetylene. In both cases the products showed quantitative yield at 1 atm and at r.t. The method is easily up-scalable in batch- and flow-modes.

Goncharova I.K., Novikov R.A., Beletskaya I.P., Arzumanyan A.V.

This study presents a highly efficient and simple recyclable catalytic system for heterophase hydrosilylation. This catalytic system consisting of a commercially available platinum precatalyst, namely K2PtCl4, and a cheap green solvent, namely ethylene glycol (EG), is easily prepared by dissolving K2PtCl4 in EG without employing ligands, additives, or inert atmosphere, at r.t. It was found that mononuclear Pt0-complex generated in the catalytic system is a single-atom catalyst. The method enables 36 recycles with quantitative yield in air at r.t. The reaction proceeds at a high rate even with small catalyst loadings. High values of TON (up to 105) and TOF (up to 106) were achieved. This approach is applicable to a wide range of unsaturated compounds, such as terminal or internal alkenes, alkynes, and alkyl-, phenyl-, and siloxy-containing hydrosilanes. Moreover, the heterophase catalytic system is suitable for synthesis of linear and cross-linked polyorganosiloxanes. In most cases, the reaction provides high yields (up to 95-99%) and selectivity. It gives mostly anti-Markovnikov products, which can be isolated from the catalytic system by simple decantation. The process is scalable to gram quantities.

Goncharova I.K., Kutumov S.P., Novikov R.A., Shiryaeva T.Y., Volodin A.D., Korlyukov A.A., Arzumanyan A.V.

This study reports the development of a selective method for the synthesis of p -tolylsiloxanes, namely, symmetrical disiloxanes and cyclotetrasiloxanes, by hydrolytic condensation of p -tolyl-containing mono(ethoxy)silanes and di(ethoxy)silanes in the presence of [Me 4 N] + OH – . The reaction occurs under mild and simple reaction conditions: at 30 °C, under atmospheric pressure, in 1–5 h, in acetone and ethanol medium or in the block (solvent-free), with a loading of 0.25–5 mol.% (per Si–OEt group) of [Me 4 N] + OH – , a commercially available and cheap catalyst. The method is well scalable and allows the target products (2a-f) to be obtained in gram amounts (up to 50 g) in 42–85% yields. The structures were confirmed using a set of physicochemical analytical methods: IR, ESI-HRMS, GPC, 3a and 4a 1 H/ 13 C/ 29 Si NMR, and X-Ray.

Goncharova I., Beletskaya I., Arzumanyan A.

This study presents a highly efficient and simple recyclable catalytic system for heterophase hydrosilylation. This catalytic system consisting of a commercially available platinum precatalyst, namely K2PtCl4, and a cheap green solvent, namely ethylene glycol (EG), is easily prepared by dissolving K2PtCl4 in EG without employing ligands, additives, or an inert atmosphere, at r.t. The suggested method allows up to 45 recycles with quantitative conversion under air at r.t. to be performed. The high reaction rate (from 2 to 20 min per cycle) and low catalyst load (0.001 – 0.1 mol%) allow high values of TON (up to ~ 104 – 105) and TOF (up to ~ 103 – 106) to be reached. This approach is applicable to a wide range of unsaturated compounds, such as functional and nonfunctional terminal or internal alkenes, alkynes, and alkyl-, phenyl-, and siloxy-containing hydride silanes. Moreover, the heterophase catalytic system is suitable for the synthesis of linear and cross-linked polyorganosiloxanes. In most cases, the reaction provides high yields (up to 95-99%) and selectivity. It gives mostly anti-Markovnikov products which can be isolated from the catalytic system by simple decantation. The process is scalable to gram quantities.

Goncharova I.K., Tukhvatshin R.S., Novikov R.A., Volodin A.D., Korlyukov A.A., Lakhtin V.G., Arzumanyan A.V.

In-depth investigation of cooperative [M]-/Organo-catalytic systems in aerobic Si−H− to Si−OH-group oxidation showed the efficiency of the two “complementary” catalytic systems, based on earth-abundant [M]-catalysts and inexpensive commercially available organic catalysts. [Co]/NHSI (A) system made it possible to oxidize a wide range of monomers but failed in the case of oligomeric and polymeric substrates. This problem was solved by application of [Cu]/NHPI (B) system.

Goncharova I.K., Ulianova E.A., Novikov R.A., Volodin A.D., Korlyukov A.A., Arzumanyan A.V.

This research presents a scalable method for chemical transformation of Si-containing derivatives of benzoic acid to a wide range of corresponding esters, thioesters, amides, etc. Some of them form HOF-like structures in the crystalline state.

Ghosh A., Reddy G.N., Siddhique P. K. M., Chatterjee S., Bhattacharjee S., Maitra R., Lyubimov S.E., Arzumanyan A.V., Naumkin A., Bhaumik A., Chowdhury B.

Compositional doping by nitrogen and sulfur into a carbon matrix with a distinct hollow sphere architecture was achieved via a simple approach and the co-doped carbon material was used as a bifunctional catalyst for an efficient CO2–epichlorohydrin cycloaddition reaction.

Platonov D.N., Kholodkov D.N., Goncharova I.K., Belaya M.A., Tkachev Y.V., Dorovatovskii P.V., Volodin A.D., Korlyukov A.A., Tomilov Y.V., Arzumanyan A.V., Novikov R.A.

This study presents a methodology for the synthesis of the ionic cyclopropenium-derived triplatinum cluster complex [(Ph3C3)2Pt3(MeCN)4]2+(BF4–)2 and its analogue with the replacement of one of the...

Kholodkov D.N., Eremchuk K.I., Soldatkin Y.V., Volodin A.D., Korlyukov A.A., Anisimov A.A., Novikov R.A., Arzumanyan A.V.

Preparation methodology for a series of hydrophobic and amphiphilic well-defined stereoregular cyclic p-tolyl-substituted siloxanes has been proposed.

Kholodkov D.N., Arzumanyan A.V., Novikov R.A., Kashin A.S., Polezhaev A.V., Vasil’ev V.G., Muzafarov A.M.

This work presents a solution to one of the most fundamentally and practically important challenges in the production of silica-based aerogels, time consumption and expensiveness of these processes, with the main focus on the sol–gel process. We suggested a highly efficient BF3-catalyzed method for the production of aerogels, which allows one to shorten the stage of the formation of a (wet) gel to 5 min, the stage of gel aging to 0, while the stage of gel workup is not required; the duration of these stages, according to the literature, ranges from days to weeks. The process is performed using commercially available, simple, and inexpensive reagents and under mild reaction conditions: BF3·Et2O as the catalyst, acetone as the solvent, room temperature, and at atmospheric pressure. This approach allows one to quickly obtain both classic opaque and transparent silica-based aerogels from Si(OMe)4 or Si(OEt)4 as well as transparent superhydrophobic ones from their mixtures with MeSi(OMe)3 or Me2Si(OMe)2. In addition, we succeeded in obtaining a series of aerogels with various organic and inorganic additives, in particular, in this way, luminescent and metallasiloxane ones were prepared. Also, the effect of the method for producing silica-based aerogels on their (supra)molecular structure and morphology was thoroughly studied by a set of physicochemical methods of analysis: scanning electron and light microscopy, X-ray microtomography, and NMR experiments. These findings allow to tune the density, transparency, mechanical strength, hydrophobicity, and other properties depending on the need by choosing the right technique.

Goncharova I.K., Tukhvatshin R.S., Kholodkov D.N., Novikov R.A., Solodilov V.I., Arzumanyan A.V.

A methodology for synthesizing a wide range of dumbbell-shaped, graft and bottlebrush polymers with all-siloxane nature (without carbosilane linkers) is suggested. These macroarchitectures are synthesized from SiOH-containing compounds—silanol (Et3SiOH) and siloxanol dendrons of the first and second generations, with various peripheral substituents (Me or Et)—and from linear siloxanes comprising terminal and internal SiH groups by the Piers–Rubinsztajn reaction. Products and key building blocks are obtained in yields up to 95%. These polymers are heat and frost-resistant siloxanes. As it turns out, the product physical properties are determined not only by the macromolecular structure, the linear chain length, the size and frequency of branched pendant, but also by the type of peripheral substituents—Me or Et—in the pendant. Thus, the viscosity of the graft polymers with branched pendant groups comprising peripheral Me-groups is more than ≈3–5 fold lower than that of analogous polymers with peripheral Et-groups.

Servesh A., Ramaraj S.G., Rajprasad J., Tabassum S., Govindaraju S.

Naranov E., Sadovnikov A., Arapova O., Guda A., Dementev K., Arzumanyan A., Kubrin G., Kholodkov D., Zagrebaev A., Wang K., Luo Z., Maximov A.

Ou J., Xu Z., Liao Q., Zhao T.

Zhang H., Duan X., Han M., Liu F., Zhang G., Gao K., Liu M.

Katayama N., Tabaru K., Nagata T., Yamaguchi M., Suzuki T., Toyao T., Jing Y., Maeno Z., Shimizu K., Watanabe T., Obora Y.

The manganese nanoparticles we synthesized demonstrated high catalytic activity, achieving 15 800 TON in the hydrosilylation of alkenes with tertiary silanes, and remained recyclable across multiple cycles.

Ashirov R., Todorovic M., Bhuvanesh N., Blümel J.

Five representatives of a novel type of di(hydroperoxy)alkane adducts of phosphine oxides have been synthesized and fully characterized, including their solubility in organic solvents. The phosphine oxide Cy3PO (1) has been used in combination with the corresponding aldehydes to create the adducts Cy3PO·(HOO)2CHCH3 (2), Cy3PO·(HOO)2CHCH2CH3 (3), Cy3PO·(HOO)2CH(CH2)2CH3 (4), Cy3PO·(HOO)2CH(CH2)3CH3 (5), and Cy3PO·(HOO)2CH(CH2)7CH3 (6). All adducts crystallize easily and contain the peroxide and phosphine oxide hydrogen-bonded in 1:1 ratios. The single crystal X-ray structures of 2–6 and their unique features are discussed. The 31P NMR spectra of the adducts 2–6 show downfield-shifted signals as compared to Cy3PO. In the IR spectra, the ν(P=O) wavenumbers of the adducts have smaller values than the neat phosphine oxide. All spectroscopic results of 2–6 show that the P=O bond is weakened by hydrogen-bonding to the di(hydroperoxy)alkane moieties. Adduct 6 selectively oxidizes PPh3 to OPPh3 within minutes, and nonanal is reformed in the process. The easy synthesis, handling, and administration of these stable, solid, and soluble peroxides with well-defined composition will have a positive impact on synthetic chemistry.

Prasad R., Singh S.K., Maity R., Ghosh P.

In this study o-phthalaldehyde is employed for the novel oxidation of a broad range of aryl methyl ketones to esters.

Tariq W., Pudukudy M., Liu Y., Li S., Zhang C., Ali Haider A., Lin L., Murtaza G., Nauman Tahir M., Zhi Y., Shan S.

Carbon dioxide (CO2) can be chemically converted into high-value products, which is not only helps to ease the environmental problems instigated by global warming and has an optimistic effect on economies around the planet. The production of cyclic carbonates is regarded as a promising approach to convert CO2 through the cycloaddition of CO2 with epoxides. However, a major obstacle in this process is the synthesis of environmentally friendly and highly effective heterogeneous catalysts. Here, a novel nitrogen-rich covalent organic framework (CP-COF) was firstly synthesized through a polymerization method of piperazine and cyanuric chloride with 1, 4‐dioxane and used for the aforesaid reaction. A number of analytical methods were employed to verify the chemical composition and the structure of the catalyst. The CP-COF catalyst possessed a significant amount of active nitrogen sites and hydrogen bond donors in it, resulting in a high level of reactivity for the cycloaddition reaction of CO2 with epichlorohydrin in the absence of any solvent and metals, and the yield of chloropropene carbonate (CPC) reached 99 % at 110 ℃, 6 h and 1 MPa CO2 pressure. The CP-COF sample exhibited commendable activity towards a range of epoxides. Moreover, it showed high reusability for the reaction without any loss in the catalytic efficiency.

Wu C., Liu J., Wu W., Wang Y., Zhao Y., Li G., Zhang Y., Zhang G.

During the synthesis of carbon-based CO2 adsorbents and supercapacitors, the introduction of nitrogen atoms into the carbon matrix has been identified as a means to enhance their performance. Nevertheless, the intricate effects of nitrogen doping on material properties pose a significant challenge in developing efficient methodologies. In this investigation, porous carbons resembling sponges were fabricated utilizing macadamia nut shells as a precursor and a dual salt comprising K2C2O4-KCl as an activating agent. Subsequent modification of the materials through ammonia post-treatment facilitated the production of nitrogen-doped porous carbon. The alterations in surface characteristics and pore morphology after ammonia treatment were meticulously examined to unravel the underlying mechanism of this modification process. The samples under scrutiny showcased remarkable CO2 adsorption capacities, peaking at 6.97 mmol/g at 0 °C and 4.65 mmol/g at 25 °C. Employing mathematical models to probe the influence of pore structure and surface properties on CO2 adsorption efficacy proved to be fruitful. A linear correlation was established to depict CO2 adsorption behavior, underscoring the joint impact of ultramicropore volume and nitrogen content on the adsorption process. Notably, the material exhibited a specific capacitance of 290.4F/g at a current density of 0.5 A/g within a three-electrode configuration, demonstrating commendable rate capability and cyclic stability. The pivotal findings from this inquiry emphasize that ammonia post-treatment represents a gentle modification strategy exerting minimal influence on the pore architecture, thereby efficaciously enhancing both CO2 adsorption and electrochemical performance.

Stoykov I.I., Antipin I.S., Burilov V.A., Kurbangalieva A.R., Rostovsky N.V., Pankova A.S., Balova I.A., Remizov Y.O., Pevzner L.M., Petrov M.L., Vasily A.V., Averin A.D., Beletskaya I.P., Nenaydenko V.G., Beloglazkina E.K., et. al.

An overview of the main scientific achievements of Russian universities in the field of organic chemistry for the period 2018–2023 is presented.

Mayorov N.S., Egorov P.A., Medvedev A.G., Mikhaylov A.A., Fatyushina E.V., Buldashov I.A., Prikhodchenko P.V.

Two polymorphs of triphenylantimony(V) bis-cumylperoxide were obtained by the interaction of triphenylantimony(V) dihalides with cumene hydroperoxide in an aromatic hydrocarbon in the presence of ammonia or aqueous potassium hydroxide solution. The structure of two polymorphic modifications I and II was determined by the single crystal X-ray diffraction analysis, revealing the crystallization in monoclinic P21/n and P21/c space groups, respectively, with Z = 4. To our knowledge, this is the first report of polymorphism of peroxo complexes. The polymorph I was characterized by elemental and thermal analyses, Fourier transform infrared and Raman spectroscopies, and powder X-ray diffraction. Analysis of crystal structure databases revealed the similarity between peroxide, hydroperoxide, and organoperoxide ligands in the corresponding p-block element complexes.

Musalov M.V.

The Special Issue “New Chemo-, Regio- and Stereoselective Reactions and Methods in Organic Synthesis” collects eight articles that have developed advanced approaches to the chemo-, regio- and stereoselective synthesis of novel important compounds, scaffolds, synthons, and practically valuable products [...]

Yadav S., Beniwal N., Singh G., Rekha P., Singh L.

Wang T., Sheng H., Xi J., Zhao Y., Jiang T., Zhao Y.

Ge Y., Cheng G., Zou Y., Ke H.

Yang H., Zhou Z., Tang C., Chen F.

The hydrosilylation of unsaturated carbon-carbon bonds is one of the most critical reactions in silicone industrial production. The homogeneous Speier's catalyst, Karstedt's catalyst, and other noble metal-based catalysts are widely used. However, simplifying the separation of the homogeneous catalyst from reaction products and reducing the high cost of precious metals is still challenging. This review describes the recent development of heterogeneous catalysts for alkene, alkyne, and allene hydrosilylations, which can effectively solve problems in homogeneous hydrosilylation.

Goncharova I.K., Beletskaya I.P., Arzumanyan A.

AbstractThis concept addresses the main economic, environmental, scientific and technological issues associated with the use of homogeneous Pt‐catalysts in the important industrial hydrosilylation process. The development of biphase catalysis is proposed as the most promising approach. One solution we suggest is the use of ethylene glycol (EG) as a medium in biphase catalysis. We have previously shown that EG in Pt‐catalyzed hydrosilylation serves not only as a medium but also as a mild reducing agent of Pt‐ions to Pt0, as well as an effective ligand for the preparation of mononuclear Pt01‐complexes. These zero valent platinum complexes are single‐atom catalysts (SAC) and have high activity in hydrosilylation, stability during storage and the ability to be recycled multiple times (~40 times). This option of using an atomic catalyst allows us to combine the advantages of homogeneous and heterogeneous catalysts.

Yang C., Tong J., Li H., Gao H., Wen G., Zhang J., Yan Y.

Goncharova I.K., Filatov S.A., Drozdov A.P., Tereshchenko A.A., Knyazev P.A., Guda A.A., Beletskaya I.P., Arzumanyan A.V.

This study presents a highly efficient and mild method for radical hydrosilylation of alkenes. The reaction proceeds under white-light, in the presence of Mn2(CO)10 pre-catalyst and HFIP as an additive, at r.t. and under air. Under white-light, [Mn]• is generated, which activates the Si–H-group to form Si• and trigger the autocatalytic process. HFIP acts as a unique activator which enables synthesis of the products with yields close to quantitative and with anti-Markovnikov selectivity. The method is applicable to terminal alkenes, including those with O-, N- and halogen-containing functional groups, styrene and allylbenzene derivatives, etc., as well as to a wide range of alkyl-, phenyl-, siloxy- and alkoxy-containing tertiary hydrosilanes. These conditions turned out to be most efficient for hydrosilylation of gaseous reagents such as ethylene and acetylene. In both cases the products showed quantitative yield at 1 atm and at r.t. The method is easily up-scalable in batch- and flow-modes.

Konopkina E., Gopin A., Pozdeev A., Chernysheva M.G., Kalle P., Pavlova E., Kalmykov S., Petrov V.G., Borisova N.E., Guda A.A., Matveev P.I.

A variant of microfluidic setup design for the study of extraction kinetics has been proposed. Mass transfer constants for Am(III) and Eu(III) and observed rate constants were obtained for N-,O-donor...

Zagrebaev A.D., Butova V.V., Guda A.A., Chapek S.V., Burov O.N., Kurbatov S.V., Vinyukova E.Y., Neganova M.E., Aleksandrova Y.R., Nikolaeva N.S., Demidov O.P., Soldatov A.V.

We developed a microfluidic synthesis with UV-Vis diagnostics using a 3D printed chip for 8,13-disubstituted berberines. This system yielded up to 30% higher product yields with high antioxidant activity compared to traditional batch synthesis.

Fei Y., Shi J., Zhou X., Zhu P., Shen R., Yang B., Yang A., Chu E.

The regulation of energy release characteristics and safety of highly active metal fuels has attracted significant attention. In response to the limitations of using hydrofluoric acid (HF) to modify zirconium (Zr) powder in batch reactors, a microfluidic method coupling ultrasound and coaxial flow microreactors was proposed to achieve the control of the microstructure on the surface of Zr powder. The fluid flow and mixing characteristics in the microreactor were analyzed using on-line detection devices, leading to the determination of suitable fluid parameters. Through analysis of the reaction process between Zr and HF, a reaction model based on the HF concentration was established and subsequently verified through a microreaction system. The results indicate that the HF concentration greatly influences the morphology and composition of Zr powder, thereby determining the material and structural transformation of the Zr powder surface. The excellent thermal oxidation performance and electrostatic safety of HF-modified Zr powder were confirmed through thermal analysis and electrostatic discharge sensitivity tests. This study provides valuable insights for controlling the microstructure and properties of ultrafine Zr powder.

Maliszewski B.P., Casillo E., Lambert P., Nahra F., Cazin C.S., Nolan S.P.

An efficient olefin hydrosilylation protocol utilising Pt(ii)–thioether-based pre-catalysts is reported.

Katayama N., Obora Y.

Hydrosilylation of alkenes is an important process in the synthesis of organosilicon compounds in which an Si–H species is added across a carbon–carbon double bond (C=C). Transition-metal catalysts, particularly those comprising noble metals, are conventionally used in hydrosilylation owing to their exceptional catalytic activities and selectivities. However, their scarcity, toxicity, and high cost (especially those of platinum catalysts) have necessitated the exploration for alternatives. Manganese, which is a low-toxic, low-cost, and earth-abundant metal, constitutes a promising substitute for precious metals in hydrosilylation reactions. Nevertheless, manganese-catalyzed alkene hydrosilylation has not been as extensively studied as that of other earth-abundant metals such as iron (Fe), cobalt (Co), and nickel (Ni). This digest paper summarizes recent advances in manganese-catalyzed hydrosilylation.

Shimada S.

This chapter summarizes recent advances of group 10 transition metal hydrosilylation catalysts from 2015 onward. Since the discovery of Speier’s catalyst in 1957, homogeneous Pt catalysts have been mainly used for the hydrosilylation reaction of C-C multiple bonds. Although research on homogeneous Pt hydrosilylation catalysts has still been intensive, recent trends of research that meet the demands for sustainable development significantly increased the research on heterogeneous and non-precious metal hydrosilylation catalysts including Ni catalysts. Although Pd catalysts are very popular in organic transformation, its usefulness in hydrosilylation reaction is relatively limited, except for several special cases such as asymmetric hydrosilylation.

Li T., Chan A.S., Meng S.

Decacarbonyldimanganese (Mn2(CO)10), one of the most long-standing organometallic reagents, bears a weak Mn-Mn bond, which occurs a homo-cleavage feasibly under heating or light-irritation, delivering an active manganese-centered radical. This highly reactive metallic radical could activate the Si-H bond, C-halogen bond, N-halogen bond, S-halogen bond, and O=O bond, generating corresponding Mn species and Si, C, N, S, and O radicals. This wonderful reactivity enables an extensive utilization of this dimeric manganese in catalytic atom-transfer reactions and oxidation reactions. In this review, we offer a comprehensive review of this growing area in recent decades. Critical comparisons and mechanism analyses are provided, along with personal perspectives for future studies.

Ondar E.E., Kostyukovich A.Y., Burykina J.V., Galushko A.S., Ananikov V.P.

A simple approach aligned with dynamic catalysis principles was successfully applied in a study of hydrosilylation reactions. The readily available Pt2dba3 complex formed a “cocktail”-type system with comparable performance to known catalysts.

Zhong T., Gu C., Li Y., Huang J., Han J., Zhu C., Han J., Xie J.

AbstractThe involvement of manganese radical for halogen atom transfer (XAT) reactions has been esteemed as one reliable method but encountered with limited catalytic models. In this paper, a novel bimetallic relay catalysis of Mn2(CO)10 and cobaloxime has been developed for divergent dehydrogenative difluoroalkylation of alkenes using commercially available difluoroalkyl bromides. A wide range of structurally diverse terminal, cyclic and internal alkenes as well as tetrasubstituted alkenes are found to be good coupling partners to deliver difluoroalkylated allylic products and difluoromethylated cyclic products, accompanied with the production of H2 as the by‐product. This bimetallic relay strategy features broad substrate scope, mild reaction conditions and excellent functional group compatibility. Its success represents an important step‐forward to expedite the construction of a rich library of difluoroalkylated products.

Shapovalov V.V., Chapek S.V., Tereshchenko A.A., Bulgakov A.N., Bagliy A.P., Volkov V.V., Konarev P.V., Soldatov M.A., Soldatov S.A., Guda A.A., Soldatov A.V.

Fine tuning of the material properties requires many trials and errors during the synthesis. The metal nanoparticles undergo several stages of reduction, clustering, coalescence and growth upon their formation. Resulting properties of the colloidal solution thus depend on the concentrations of the reagents, external temperature, synthesis protocol and qualification of the researcher determines the reproducibility and quality. Automatized flow systems overcome the difficulties inherent for the conventional batch approaches. Microfluidic systems represent a good alternative for the high throughput data collection. The recent advances in 3D-printing made complex topologies in microfluidic devices cheaper and easily customizable. However, channels of the cured photopolymer resin attract metal ions upon synthesis and create crystallization centers. In our work we present 3D-printed system for the noble metal nanoparticle synthesis in slugs. Alternating flows of oil and aqueous reaction mixtures prevent metal deposition on the channel walls. Elongated droplets are convenient for optical and X-ray diagnostics using conventional methods. We demonstrate the work of the system using Ag nanoparticles synthesis for machine-learning assisted tuning of the plasmon resonance frequency.

Jia N., Torres de Oliveira L., Bégin-Drolet A., Greener J.

Infrared spectroscopy combined with customized microfluidic reactor yields the SpectIR-fluidic reactor. We validate the tool using a proton transfer reaction and demonstrate its ability to follow reactions after just 130 milliseconds of mixing.