Hydrosilylation of alkenes and ketones catalyzed by nickel(II) indenyl complexes

2003 ◽  
Vol 81 (11) ◽  
pp. 1299-1306 ◽  
Author(s):  
Frédéric-Georges Fontaine ◽  
René-Viet Nguyen ◽  
Davit Zargarian
Keyword(s):  
Reaction Mechanism ◽  
Key Words ◽  
Room Temperature ◽  
Active Species ◽  
The Other ◽  
Silyl Ethers ◽  
Cationic Species ◽  
Catalytically Active ◽  
High Yields ◽  
Indenyl Complexes

Abstraction of Cl– from the complexes (indenyl)Ni(PPh3)Cl generates cationic species that are effective precatalysts for the hydrosilylation of some olefins and ketones. For instance, the mixture of (1-Me-indenyl)Ni(PPh3)Cl and NaBPh4 (or methylaluminoxane) reacts at room temperature with ca. 100 equiv. each of PhSiH3 and styrene to produce [1-phenyl-1-ethyl](phenyl)silane, PhCH(CH3)(SiPhH2), in 50%–80% yield. The same system can also catalyze the hydrosilylation of 1-hexene and norbornene, but the products arising from these substrates consist of mixtures of regio- and stereoisomers. On the other hand, ketone hydrosilylation is regiospecific, giving the corresponding silyl ethers in high yields. A number of experimental observations have indicated that the initially generated Ni-based cation is not the catalytically active species. Indeed, the cationic initiators may be replaced by LiAlH4 or AlMe3, which generate the corresponding Ni-H or Ni-Me derivatives, respectively. Moreover, the observed regioselectivity for the addition of PhSiH3 to styrene (i.e., predominant addition of the silyl fragment to the α-C) is opposite of what would be expected if the reaction mechanism involved carbocationic intermediates. A new mechanism is proposed in which the active species is a Ni-H species originating from the transfer of H– from PhSiH3 to the initially generated Ni cation. Key words: hydrosilylation, nickel indenyl complexes, cationic complexes, hydride intermediates.

scholarly journals Synthesis of spiro[dihydropyridine-oxindoles] via three-component reaction of arylamine, isatin and cyclopentane-1,3-dione

2013 ◽  
Vol 9 ◽  
pp. 8-14 ◽  
Author(s):  
Yan Sun ◽  
Jing Sun ◽  
Chao-Guo Yan
Keyword(s):  
Acetic Acid ◽  
Reaction Mechanism ◽  
Room Temperature ◽  
The Other ◽  
Other Hand ◽  
Three Component Reaction ◽  
High Yields

A fast and convenient protocol for the synthesis of novel spiro[dihydropyridine-oxindole] derivatives in satisfactory yields was developed by the three-component reactions of arylamine, isatin and cyclopentane-1,3-dione in acetic acid at room temperature. On the other hand the condensation of isatin with two equivalents of cyclopentane-1,3-dione gave 3,3-bis(2-hydroxy-5-oxo-cyclopent-1-enyl)oxindole in high yields. The reaction mechanism and substrate scope of this novel reaction is briefly discussed.

Sewage sludge as a precursor of adsorbents/catalysts for environmental applications

2007 ◽  
Vol 2 (1) ◽  
Author(s):  
A. Ros ◽  
C. Canals-Batlle ◽  
M.A. Lillo-Ródenas ◽  
E. Fuente ◽  
M. A. Montes-Morán ◽  
...  
Keyword(s):  
Sewage Sludge ◽  
Room Temperature ◽  
Waste Water Treatment ◽  
Textural Properties ◽  
Active Species ◽  
Elemental Sulphur ◽  
Gaseous Emissions ◽  
Removal Experiments ◽  
Catalytically Active

This paper focuses on the valorisation of solid residues obtained from the thermal treatment of sewage sludge. In particular, sewage sludge samples were collected from two waste water treatment plants (WWTPs) with different sludge line basic operations. After drying, sludges were heated up to 700 °C in appropriate ovens under diluted air (gasification) and inert (pyrolysis) atmospheres. The solids obtained, as well as the dried (raw) sludges, were characterised to determine their textural properties and chemical composition, including the speciation of their inorganic fraction. All the materials under study were employed as adsorbents/catalysts in H2S removal experiments at room temperature. It was found that, depending on the particular sludge characteristics, outstanding results can be achieved both in terms of retention capacities and selectivity. Some of the solids outperform commercially available sorbents specially designed for gaseous emissions control. In these adsorbents/catalysts, H2S is selectively oxidised to elemental sulphur most likely due to the presence of inorganic, catalytically active species. The role of the carbon-enriched part on these solids is also remarked.

Iodosulfonation of alkenes with benzenesulfinic acid – N-iodosuccinimide — Facile preparation of α,β-unsaturated sulfones

2006 ◽  
Vol 84 (4) ◽  
pp. 667-675 ◽  
Author(s):  
Russell R Wolff ◽  
Vikram Basava ◽  
Robert M Giuliano ◽  
Walter J Boyko ◽  
J Herman Schauble
Keyword(s):  
Room Temperature ◽  
High Yield ◽  
Allylic Alcohols ◽  
Neutral Alumina ◽  
Silyl Ethers ◽  
Step Procedure ◽  
Ferrier Rearrangement ◽  
Facile Preparation ◽  
High Yields ◽  
Yield And Purity

Reaction of alkenes and alkenols with N-iodosuccinimide (NIS) and benzenesulfinic acid in dichloromethane at room temperature affords vic-iodophenylsulfonyl adducts in good to high yields. Treatment of the iodosulfones with neutral alumina in dichloromethane at room temperature results in dehydroiodination to give the corresponding vinyl sulfones in high yield and purity by this convenient two-step procedure. Application of the iodosulfonation–dehydroiodination sequence to allylic alcohols and silyl ethers gave γ-oxygenated, α,β-unsaturated phenylsulfones, while the attempted iodosulfonation of glycals, as intermediates to vinyl sulfones, resulted in addition of benzenesulfinic acid with double bond shift (Ferrier rearrangement). Key words: iodosulfonation, vinyl sulfones, benzenesulfinic acid, N-iodosuccinimide, dehydroiodination.

An ESR study of irradiated mixtures of hydrogen peroxide and Cu(II) complexes at 77 K

1988 ◽  
Vol 53 (12) ◽  
pp. 3080-3088 ◽  
Author(s):  
Pavel Stopka
Keyword(s):  
Hydrogen Peroxide ◽  
High Pressure ◽  
Catalytic Activity ◽  
Oxalic Acid ◽  
Hydroxyl Radicals ◽  
Room Temperature ◽  
Active Species ◽  
Mercury Lamp ◽  
Catalytically Active ◽  
High Concentrations

When aqueous solutions containing hydrogen peroxide and CuSO4 are irradiated by a high-pressure mercury lamp at room temperature and at 77 K, hydrogen peroxide decomposes and hydroxyl radicals generated in high concentrations coordinate to CuSO4. The catalytic activity of Cu(II), which depends on the choice of the ligand (triene, diene, ethylenediamine, ammonia, EDTA, oxalic acid and glycerine) and the proportion between the monomeric and dimeric forms of the Cu(II) complex, shows a maximum at a concentration of 10-4 mol dm-3. The catalytically active species is the monomeric Cu(II) complex, the dimer being inactive.

MERCURY PHOTOSENSITIZED DECOMPOSITION OF ETHYLENE OXIDE

1955 ◽  
Vol 33 (11) ◽  
pp. 1684-1695 ◽  
Author(s):  
R J Cvetanović
Keyword(s):  
Reaction Mechanism ◽  
Ethylene Oxide ◽  
Room Temperature ◽  
Small Extent ◽  
The Other ◽  
Hydrogen Atoms ◽  
Molecular Process ◽  
Complete Reaction ◽  
General Similarity

Some aspects of the mercury photosensitized decomposition of ethylene oxide at room temperature have been reinvestigated. At least two, and probably more than two, distinct primary steps occur. The previously assumed major primary formation of hydrogen by a molecular process is shown to occur to a relatively small extent only. Hydrogen atoms play an important role in the process, as well as the following radicals: CH3, CHO, CH2CHO, and C2H5, and probably to a lesser extent also CH2. The products formed are CO, H2, C2H6, a little CH2CO and C2H4, and large amounts of aldehydes. The presence of higher aldehydes has been demonstrated. While there is a general similarity to the other modes of decomposition of ethylene oxide, a unique and unambiguous solution of the complete reaction mechanism is at present not possible.

scholarly journals Vitamin B12-catalyzed synthesis of some peracetylated alkyl β-D-xylopyranosides

2003 ◽  
Vol 68 (10) ◽  
pp. 719-722 ◽  
Author(s):  
Zorica Petrovic ◽  
Dejan Andjelkovic ◽  
Ljiljana Stevanovic
Keyword(s):  
Vitamin B12 ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Reductive Elimination ◽  
Active Species ◽  
Catalytically Active ◽  
Glycosylation Reaction ◽  
Moderate Yield

The vitamin B12-catalyzed glycosylation reaction of brominated ?-D-xylose peracetate with alkanols ROH (C1-C8) has been studied. The catalytically active species in this reaction was cob(I)alamin, obtained by chemical reduction of Vitamin B12 with NaBH4 (Co(III) to Co(I)). The reaction was carried out with 2 mol% of vitamin B12, with respect to xylosyl bromide 1 under argon at room temperature. Under these conditions, peracetylated C1-C8-alkyl ?-D-xylopyranosides (3a?3f) were obtained in moderate yield (55?70 %). In all cases 3,4-di-O-acetyl-D-xylal (4) was obtained, as the product of reductive elimination of peracetylated xylosyl bromide (15?25 %).

Electron microscope studies of the plastic deformation of ternary alloys based on GaAs

1990 ◽  
Vol 48 (4) ◽  
pp. 1120-1120
Author(s):  
R. Haswell ◽  
U. Bangert ◽  
P. Charsley
Keyword(s):  
Plastic Deformation ◽  
Electron Microscope ◽  
Room Temperature ◽  
Stacking Faults ◽  
The Other ◽  
Ternary Alloys ◽  
Dislocation Mobility ◽  
Semiconducting Materials ◽  
Micro Indentation

A knowledge of the behaviour of dislocations in semiconducting materials is essential to the understanding of devices which use them . This work is concerned with dislocations in alloys related to the semiconductor GaAs . Previous work on GaAs has shown that microtwinning occurs on one of the <110> rosette arms after indentation in preference to the other . We have shown that the effect of replacing some of the Ga atoms by Al results in microtwinning in both of the rosette arms.In the work to be reported dislocations in specimens of different compositions of Gax Al(1-x) As and Gax In(1-x) As have been studied by using micro indentation on a (001) face at room temperature . A range of electron microscope techniques have been used to investigate the type of dislocations and stacking faults/microtwins in the rosette arms , which are parallel to the [110] and [10] , as a function of composition for both alloys . Under certain conditions microtwinning occurs in both directions . This will be discussed in terms of the dislocation mobility.

HAYNES STELLITE ALLOY No. 98M2

Alloy Digest ◽  
1960 ◽  
Vol 9 (7) ◽  
Keyword(s):  
Fracture Toughness ◽  
Compressive Strength ◽  
Physical Properties ◽  
Room Temperature ◽  
Base Alloy ◽  
Heat Treating ◽  
The Other ◽  
Stellite Alloy ◽  
Cobalt Base Alloy ◽  
Cobalt Base

Abstract HAYNES STELLITE 98M2 Alloy is a cobalt-base alloy having higher compressive strength and higher hardness than all the other cobalt-base alloys at room temperature and in the red heat range. This datasheet provides information on composition, physical properties, hardness, elasticity, tensile properties, and compressive strength as well as fracture toughness. It also includes information on heat treating, machining, and joining. Filing Code: Co-22. Producer or source: Haynes Stellite Company.

HISTOPATHOLOGY OF THE PIGMENTED TUMORAL-LIKE LESIONS OF THE SKIN AT HUE HOSPITAL OF MEDICINE AND PHARMACY UNIVERSITY

2018 ◽  
Vol 8 (4) ◽  
pp. 65-69
Author(s):  
Mao Nguyen Van ◽  
Dong Tran Nam
Keyword(s):  
Key Words ◽  
Definitive Diagnosis ◽  
The Other ◽  
Cell Tumour ◽  
Cross Sectional ◽  
Skin Tumour ◽  
Clinical Appearance ◽  
The Face ◽  
The Common ◽  
Difficult Cases

Background: Pigmented tumour of the skin is one of the common tumour in human including the benign pigmented tumours (more common) called Nevi tumours and the malignant one called melanoma which was less frequent but the most poor in prognosis. In addition, the others not belonging to these group had the same clinical appearance, so the application of histopathology and immunohistochemistry for the definitive diagnosis was indespensible. Objectives: 1. To describe the macroscopic features of the pigmented tumoral-like lesions; 2. To classify the histopathologic types of the pigmented cell tumours and the other pigmented tumours of the skin. Materials and Method: Cross-sectional research on 55 patients diagnosed as pigmented tumoral lesions by clinician, then all definitively diagnosed by histopathology combining the immunohistochemistry in difficult cases. Results: There was no difference in gender, the disease was discovered most common in adult, especially with the age over 51 years old (58.1%). the most region located was in the face accounting for 60%, following the trunk and limbs (14.6%, 12.8% respectively). All 3 malignant melanomas happened in foot. The most common color of the lesions was black (65.4%), the other ones were rose, grey and blue. Histopathology and immunohisthochemistry showed that the true pigmented cell tumours were 52.6% encompassing benign ones (Nevi tumour) (41.8%), melanoma (5.4%) and lentigo (5.4%). 47.4% was not the true pigmented cell tumour including pigmented basocellular carcinoma (36.4%) and the others less common as histiofibromas, acanthoma and papilloma. Conclusion: the pigmented tumoral-like lesions of the skin could be the true pigmented cell tumours and the others, so the application of the histopathology and the immunohistochemistry after the clinical discovery helps to determine and classify the disease definitely and for the best orientation of treatment as well. Key words: skin tumour, benign pigmented tumour (Nevi), malignant pigmented tumour (melanoma), pigmented basocellular carcinoma

The Reactivity of Different Active Forms of Sodium Carbonate with Respect to Sulfur Dioxide

1992 ◽  
Vol 57 (11) ◽  
pp. 2302-2308
Author(s):  
Karel Mocek ◽  
Erich Lippert ◽  
Emerich Erdös
Keyword(s):  
Thermal Decomposition ◽  
Liquid Phase ◽  
Sulfur Dioxide ◽  
Specific Surface ◽  
Surface Area ◽  
Sodium Carbonate ◽  
Room Temperature ◽  
Active Form ◽  
The Other ◽  
Kinetics Of

The kinetics of the reaction of solid sodium carbonate with sulfur dioxide depends on the microstructure of the solid, which in turn is affected by the way and conditions of its preparation. The active form, analogous to that obtained by thermal decomposition of NaHCO3, emerges from the dehydration of Na2CO3 . 10 H2O in a vacuum or its weathering in air at room temperature. The two active forms are porous and have approximately the same specific surface area. Partial hydration of the active Na2CO3 in air at room temperature followed by thermal dehydration does not bring about a significant decrease in reactivity. On the other hand, if the preparation of anhydrous Na2CO3 involves, partly or completely, the liquid phase, the reactivity of the product is substantially lower.

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