“…A comparison of the reactivity of 11 and 43 toward acetylenic compounds was motivated by the ability of the former to catalyze ethylene oligomerization. In this case, ethylene insertion into the Ni−Ph bond of 11 is the key step affording, after β-hydride elimination, the active species containing a Ni−H bond. ,, Similarly, DMAD inserts into the Ni−Ph bond of 11 to give 66 (eq 31), and likewise for diphenylacetylene or CO 2 . , 17 Formation of C(enolate)N Bonds by Reaction of Phosphinoenolate Pd(II) Complexes with RNNR (R = CO 2 Et) 109 …”
Section: 4 Reactions With Alkynes Tetracyanoethylene
and Azo Compound...mentioning
confidence: 99%
“…33,63,64 Similarly, DMAD inserts into the Ni-Ph bond of 11 to give 66 (eq 31), and likewise for diphenylacetylene or CO 2 . 64,107 In contrast to the classical methods used to generate a metal-alkenyl bond by alkyne insertion into a M-C or M-H bond, those described here did not involve a carbon center directly bonded to the metal. In summary, all three types of isomeric structures T through V have been encountered (Scheme 16).…”
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
“…A comparison of the reactivity of 11 and 43 toward acetylenic compounds was motivated by the ability of the former to catalyze ethylene oligomerization. In this case, ethylene insertion into the Ni−Ph bond of 11 is the key step affording, after β-hydride elimination, the active species containing a Ni−H bond. ,, Similarly, DMAD inserts into the Ni−Ph bond of 11 to give 66 (eq 31), and likewise for diphenylacetylene or CO 2 . , 17 Formation of C(enolate)N Bonds by Reaction of Phosphinoenolate Pd(II) Complexes with RNNR (R = CO 2 Et) 109 …”
Section: 4 Reactions With Alkynes Tetracyanoethylene
and Azo Compound...mentioning
confidence: 99%
“…33,63,64 Similarly, DMAD inserts into the Ni-Ph bond of 11 to give 66 (eq 31), and likewise for diphenylacetylene or CO 2 . 64,107 In contrast to the classical methods used to generate a metal-alkenyl bond by alkyne insertion into a M-C or M-H bond, those described here did not involve a carbon center directly bonded to the metal. In summary, all three types of isomeric structures T through V have been encountered (Scheme 16).…”
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
“…Besonders interessant erscheint es auch, Kohlendioxid mit mehreren Olefin-Molekulen zu langkettigen Carbonsauren zu verknupfen. Erste stochiometrische Reaktionen mit C 0 2 und Ethen an Nickel-Komplexen enviesen sich als moglich [96]. Im Gegensatz zu den Reaktionen des C02 mit Monoenen verlaufen die Reaktionen mit 1,3-Dienen wesentlich erfolgreicher.…”
Use of carbon dioxide in industrial organic syntheses. Although carbon dioxide is important as an abundant carbonaceous raw material, its utilization in chemical processes so far has been rather limited. This review covers the reactions of CO2 employed in industry, such as the production of urea, the Kolbe‐Schmitt reaction, the synthesis of cyclic organic carbonates, and the use of CO2 in methanol synthesis. Interesting recent developments in CO2 chemistry, especially the transition metal catalyzed reactions, are also elucidated. In addition to the synthesis of polymers and hydrocarbons, the production of oxygen‐containing chemicals seems to be very profitable and attractive for future industrial applications. Not only can derivatives of formic acid and carbonic acid be formed but longer‐chain carboxylic acids and their derivatives are also accessible by reactions of carbon dioxide with hydrocarbons such as alkynes, alkenes, and 1,3‐dienes.
“…Stoichiometric [18,19] as well as catalytic [20] reactions leading to C-C bonds under CO 2 incorporation evolved in the following years. As a result of his early studies in Aachen Arno Behr published a monograph that formed the leading reference in the field for many years to come [12].…”
Dedicated to Professor Heribert Offermanns on the occasion of his 75 th birthdayWith the growing perception of industrialized societies that fossil raw materials are limited resources, academic chemical research and chemical industry have started to introduce novel catalytic technologies which aim at the development of economically competitive processes relying much more strongly on the use of alternative carbon feedstocks. Great interest is given world-wide to carbon dioxide (CO 2 ) as it is part of the global carbon cycle, nontoxic, easily available in sufficient quantities anywhere in the industrialized world, and can be managed technically with ease, and at low cost. In principle carbon dioxide can be used to generate a large variety of synthetic products ranging from bulk chemicals like methanol and formic acid, through polymeric materials, to fine chemicals like aromatic acids useful in the pharmaceutical industry. Owing to the high thermodynamic stability of CO 2 , the energy constraints of chemical reactions have to be carefully analyzed to select promising processes. Furthermore, the high kinetic barriers for incorporation of CO 2 into C-H or C-C bond forming reactions require that any novel transformation of CO 2 must inevitably be associated with a novel catalytic technology. This short review comprises a selection of the most recent academic and industrial research developments mainly with regard to innovations in CO 2 chemistry in the field of homogeneous catalysis and processes.
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