Formation and hydrogen release of hydrazine bisborane: transfer vs. attachment of a borane

The reactivity of hydrazine in the presence of diborane has been investigated using ab initio quantum chemical computations (MP2 and CCSD(T) methods with the aug-cc-pVTZ basis set). Portions of the relevant potential energy surface were constructed to probe the formation mechanism of the hydrazine diborane (BH(3)BH(3)NH(2)NH(2)) and hydrazine bisborane (BH(3)NH(2)NH(2)BH(3)). The differences between both adducts are established. The release of hydrogen molecules from hydrazine bisborane adducts has also been characterized. Our results suggest that the BH(3)NH(2)NH(2)BH(3) adduct, which has been prepared experimentally, is formed from the starting reactants hydrazine + diborane. The observed adduct is produced by a transfer of a BH(3) group from BH(3)BH(3)NH(2)NH(2) rather than by the direct attachment of a separate BH(3) group, generated by predissociation of diborane, to BH(3)NH(2)NH(2).     

Catalytic synthesis of lithium hydride under mild conditions

A catalyst composed of titanium tetrachloride and naphthalene or its methyl derivatives with very high activity was found for the synthesis of LiH. Metallic lithium can be quantitatively hydrogenated to lithium hydride at 25–50°C under atmospheric pressure within 2–5 h according to various catalyst compositions. The catalyst stability was investigated and the relationship between catalyst compositions and reaction controlling step was established also.     

温和条件下氢化锂的催化合成

本文提出了一种温和条件下合成氢化锂的方法,催化剂是由萘或萘的甲基衍生物和TiCl4组成,具有很高的活性。它可以使金属锂在25-50℃常压加氢,根据催化剂的不同组成,锂可以在2～5小时内定量地转化成氢化锂,考察了催化剂的稳定性,并确定了催化剂组成和控制反应步骤之间的关系。     

Polarizing the Nazarov cyclization: efficient catalysis under mild conditions

Substituted divinyl ketones were studied in the Nazarov cyclization. alpha-Carbomethoxy divinyl ketones underwent efficient Nazarov cyclization with catalytic copper triflate (2 mol %) to give a single cyclopentenone regio- and stereoisomer. The efficiency of the cyclizations correlated with the ability of the substituents to favorably polarize the pi-system of the cationic intermediate.     

Organic crystals absorb hydrogen gas under mild conditions

We have studied the hydrogen sorption on three well-known organic hosts that possess vacant lattice voids large enough to accommodate H2 molecules.     

High efficient iron-catalyzed transfer hydrogenation of quinolines with Hantzsch ester as hydrogen source under mild conditions

A highly efficient transfer hydrogenation of quinolines with Hantzsch ester as hydrogen source in the presence of 1 mol% Fe(OTf)₂ under mild conditions has been developed. A series of substituted 1,2,3,4-tetrahydroquinoline derivatives were afforded in excellent yields with good functional group tolerance.     

Facile recycling of anhydride-cured epoxy thermoset under mild conditions with multifunctional hydrazine hydrate

Environmental economics is accelerating the urgency to develop recycling technologies for the ever-growing quantity of discarded thermoset polymers. Herein, we developed a mild and energy-saving process for high-efficiency degradation and reuse of anhydride-cured epoxy thermoset with the aid of hydrazine hydrate. The degradation degree of the epoxy resin reached 99.6% at 120 °C within a short time of 60 min. During the reaction, the ester bonds in the cross-linked network were selectively cleaved by the amination of hydrazine hydrate, and the epoxy resin was fully converted to new monomers that contained hydrazide and hydroxyl groups, respectively. Moreover, the degradation mechanism of the epoxy resin in hydrazine hydrate was studied and a nucleation model was utilized to predict the actual degradation behavior of the system. Finally, the degradation products can be directly mixed with epoxy precursor to prepare a new waterborne epoxy coating with good comprehensive properties. This work not only demonstrates a new way to realize the efficient degradation of epoxy resins, but also provides a facile and efficient recycling protocol for thermosets.     

温和条件下甲烷在熔盐介质中的催化转化

利用硝酸根-硝酸钾(摩尔比0.62:0.38)的熔盐体系作反应介质,以CeO~2,Ce(SO~4)~2,Cu(CF~3CO~2)~2,Co(CF~3CO~2)等为催化剂,在160℃和6.0MPa条件下甲烷被氧化成丙酮和/或三氟醋酸甲酯。甲烷的氯化则可在含氯化铜的氯化铝-氯化钠(摩尔比1:1)的熔盐介质中进行,硫酸银的引入可提高甲烷转化率和一氯甲烷的选择性。     

Hydrogen generation from methanol reforming under unprecedented mild conditions

A homogeneous catalyst [Cp^*Rh(NH₃)(H₂O)₂]³⁺ has been found for the clean conversion of methanol and water to hydrogen and carbon dioxide.The simple and easily available reaction steps can circumvent the formation of CO,therefore,making it possible to avoid inactivating catalysts and contaminating the hydrogen fuel.Different from conventional reforming method for hydrogen production,no additional alkaline or organic substances are required in this method.Valuable hydrogen can be obtained under ambient pressure at 70℃,corresponding TOF is 83.2 h^-1.This is an unprecedented success in reforming methanol to hydrogen.Effects of reaction conditions,such as reaction temperature,initial methanol concentration and the initial pH value of buffer solution on the hydrogen evolution are all systematically investigated.In a certain range,higher reaction temperature will accelerate reaction rate.The slightly acidic condition is conducive to rapid hydrogen production.These findings are of great significance to the present establishment of the carbon-neutral methanol economy.     

Tris(pentafluorophenyl)borane: a mild and efficient catalyst for the chemoselective tritylation of alcohols

An efficient acid-catalyzed protection of alcohols as trityl ethers is described using triphenylmethanol in the presence of tris(pentafluorophenyl)borane (3 mol %) in dichloromethane at room temperature. The chemoselectivity of this protocol is demonstrated by studying the tritylation of a primary alcohol in the presence of a secondary alcohol and also the mildness of this catalyst was studied with substrates containing acid labile protecting groups.     

Catalytic oxidation of alcohols with polymer-supported ruthenium complex under mild conditions

Polymer-supported ruthenium-containing complex PS–Phen–Ru was synthesized (where PS = chloromethyl polystyrene resin, Phen = 1,10-phenanthroline) and was characterized by FT-IR, ICP, and XPS. The supported complex was used to catalyze the oxidation of primary aliphatic alcohols as well as aromatic alcohols in the presence of iodosylbenzene. The oxidations were carried out in acetonitrile solution, affording the corresponding aldehydes or ketones in high substrate conversion and high selectivities under mild reaction conditions. The catalyst can be easily prepared and can be recycled.     

Three-dimensional nitrogen-doped graphene hydrogel supported Co-CeOx nanoclusters as efficient catalysts for hydrogen generation from hydrolysis of ammonia borane

Benefit from the strong synergistic electronic effect between Co and CeO_x, as well as the strong metalsupport interaction between Co-CeO_x and 3D NGH, the as-synthesized Co-(CeO_x)_0.91/NGH catalyst exhibits excellent catalytic activity toward hydrolysis of ammonia borane, with the turnover frequency (TOF) value of 79.5 min^-1.     

NiPt nanoparticles supported on CeO2 nanospheres for efficient catalytic hydrogen generation from alkaline solution of hydrazine

Thanks to the strong electronic interaction and support-metal interaction between NiPt and spherical CeO₂, the obtained Ni₅Pt₅-CeO₂ catalyst exhibits superior catalytic performance for hydrogen generation from alkaline solution of hydrazine at room temperature.     

Cellulose supported ruthenium nanoclusters as an efficient and recyclable catalytic system for benzene hydrogenation under mild conditions

Ruthenium nanoclusters supported on biopolymer cellulose were prepared by chemical reduction technique and characterized by various experimental tools. The cellulose supported Ru catalyst effectively hydrogenates benzene under mild and solvent free conditions. The complete conversion of benzene to cyclohexane was achieved at 70°C and 2.0 MPa partial pressure of H₂ in 1 h. Effect of various parameters such as reaction temperature, H₂ partial pressure, metal loading and catalyst amount on hydrogenation of benzene was studied in detail. The catalyst was recovered from product and reused upto four times without significant loss in its catalytic activity.

     

Catalytic synthesis of aldehydes and ketones under mild conditions using TEMPO/Oxone

[formula: see text] A novel, metal-free oxidation system for the catalytic synthesis of aldehydes and ketones--TEMPO/Oxone--has been developed. An optimized reaction protocol proved especially successful for the synthesis of ketones. Additionally, the influence of quarternary ammonium salts on the catalysis was studied. The mild conditions of this novel procedure were shown to tolerate even sensitive silyl protective groups which can otherwise be cleaved in the presence of Oxone.     

Complexes of borane and N-heterocyclic carbenes: a new class of radical hydrogen atom donor

Calculations suggest that complexes of borane with N-heterocyclic carbenes (NHC) have B-H bond dissocation energies more then 20 kcal/mol less than free borane, diborane, borane-THF, and related complexes. Values are in the range of popular radical hydrogen atom donors like tin hydrides (70-80 kcal/mol). The resulting prediction that NHC borane complexes could be used as radical hydrogen atom donors was verified by radical deoxygenations of xanthates by using either AIBN or triethylborane as initiator.