Aktivierung von kohlendioxid an übergangsmetallzentren: Metallaringschluss mit dicyclopentadien am elektronenreichen nickel(0)-komplexrumpf als topo- und stereoselektive reaktion

Walther, Dirk; Dinjus, E.; Sieler, Joachim; Andersen, Leif; Lindqvist, Oliver

doi:10.1016/0022-328x(84)80607-5

Cited by 45 publications

(13 citation statements)

References 20 publications

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“…This reaction has been an object of extensive studies by the teams of Hoberg and Walther since the early 1980s. [20,21] Yet, in all reactions, stable metallalactones are formed, which do not undergo b-hydride elimination due to the ring strain. Thus, nearly all reports include the product cleavage by acids and hence, complex destruction, rendering the reactions intrinsically non-catalytic.…”

Section: Acrylic Acid From Co 2 and Ethylenementioning

confidence: 99%

Recycling CO₂? Computational Considerations of the Activation of CO₂ with Homogeneous Transition Metal Catalysts

2012

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Faced with depleting fossil carbon sources, the search for alternative energy carriers and energy storage possibilities has become an important issue. Nature utilizes carbon dioxide as starting material for storing sun energy in plant hydrocarbons. A similar approach, storing energy from renewable sources in chemical bonds with CO2 as starting material, may lead to partial recycling of CO2 created by human industrial activities. Unfortunately, currently available routes for the transformation of CO2 involve high temperatures and are often not selective. With the development of more sophisticated methods and better software, theoretical studies have become both increasingly widespread and useful. This concept article summarizes theoretical investigations of the current state of the feasibility of CO2 activation with molecular transition metal catalysts, highlighting the most promising reactions of CO2 with olefins to industrially relevant acrylic acid/acrylates, and the insertion of CO2 into metal–element bonds, particularly for the synthesis of cyclic carbonates and polymers. Rapidly improving computational power and methods help to increase the importance and accuracy of calculations continuously and make computational chemistry a useful tool helping to solve some of the most important questions for the future.

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Section: Acrylic Acid From Co 2 and Ethylenementioning

confidence: 99%

Recycling CO₂? Computational Considerations of the Activation of CO₂ with Homogeneous Transition Metal Catalysts

2012

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“…For example, it was revealed that a very common pathway of CO 2 activation at Ni(0) metal centers proceeds via the formation of five-memberedring nickelalactones. These compounds have been isolated and characterized via X-ray diffraction analysis in various studies [37,44]. This enabled the possibility to study their reactivity toward further insertion reactions separately.…”

Section: Reactions With Group 10 Metalsmentioning

confidence: 99%

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

Brill

Lazreg

Cazin

et al. 2015

Topics in Organometallic Chemistry

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The development of sustainable chemical processes is a long-standing challenge. Carbon dioxide represents a renewable C1 building block for organic synthesis and industrial applications as an alternative to other common feedstocks which are based on natural gas, petroleum oil, or coal. Apart from the advantages associated with the nontoxicity and abundance of CO 2 , its utilization further enables the reduction in its atmospheric content, which contributes significantly to the greenhouse effect. Although widespread application of CO 2 in organic synthesis -even on an industrial scale -will not be able to fully compensate for the steadily increasing atmospheric quantities produced (mainly by the combustion of fuels), ecological and economical factors make its usage highly desirable. Therefore, tremendous efforts toward activation and utilization of CO 2 have been made by the scientific community over the last 30 years, and, as a result, the number of highly efficient transition metal-catalyzed CO 2 -incorporative reactions has increased dramatically, especially within the last decade. The achievements in the development of sustainable and economic chemical processes for the carboxylation of organic molecules with CO 2 are presented in detail in this chapter.

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“…Die Reaktionen lieferten stabile Nickelalactone bei Raumtemperatur in THF-Lçsung (Schema 3). [11][12][13][14] Üblicherweise wurden Nickel(0)-Olefin-Komplexe wie [Ni(h 4cod) 2 ] [15] oder [Ni(h 6 -cdt)] [16] als Vorstufen für die Reaktion mit sterisch anspruchsvollen s-Donorliganden wie Phosphanen bzw. zweizähnigen Liganden (dcpe, bipy usw.)…”

Section: Koordination Von Co 2 An üBergangsmetallkomplexeunclassified

Umwandlung von Kohlendioxid mit Übergangsmetall‐Homogenkatalysatoren: eine molekulare Lösung für ein globales Problem?

et al. 2011

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In der Vergangenheit wurde eine Vielzahl von Methoden zur Verwendung von Kohlendioxid in der organischen Synthese entwickelt. Trotz der breiten Gesamtverfügbarkeit von CO2 auf der Erde ist sein Einsatz als Reaktant, insbesondere in der Synthesechemie, recht selten. In den letzten 35 Jahren wurde intensiv daran geforscht, kosten‐ und energieeffiziente katalytische Prozesse zu finden, um CO2 zu Carbonsäuren, Estern, Lactonen und Polymeren umzusetzen. Dieser Aufsatz fasst die bis heute vorhandenen homogenkatalytischen Routen zur Verwendung von CO2 als C1‐Kohlenstoffquelle für die Synthese industrieller Produkte sowie Feinchemikalien zusammen.

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Aktivierung von kohlendioxid an übergangsmetallzentren: Metallaringschluss mit dicyclopentadien am elektronenreichen nickel(0)-komplexrumpf als topo- und stereoselektive reaktion

Cited by 45 publications

References 20 publications

Recycling CO₂? Computational Considerations of the Activation of CO₂ with Homogeneous Transition Metal Catalysts

Recycling CO₂? Computational Considerations of the Activation of CO₂ with Homogeneous Transition Metal Catalysts

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

Umwandlung von Kohlendioxid mit Übergangsmetall‐Homogenkatalysatoren: eine molekulare Lösung für ein globales Problem?

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Aktivierung von kohlendioxid an übergangsmetallzentren: Metallaringschluss mit dicyclopentadien am elektronenreichen nickel(0)-komplexrumpf als topo- und stereoselektive reaktion

Cited by 45 publications

References 20 publications

Recycling CO2? Computational Considerations of the Activation of CO2 with Homogeneous Transition Metal Catalysts

Recycling CO2? Computational Considerations of the Activation of CO2 with Homogeneous Transition Metal Catalysts

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

Umwandlung von Kohlendioxid mit Übergangsmetall‐Homogenkatalysatoren: eine molekulare Lösung für ein globales Problem?

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Recycling CO₂? Computational Considerations of the Activation of CO₂ with Homogeneous Transition Metal Catalysts

Recycling CO₂? Computational Considerations of the Activation of CO₂ with Homogeneous Transition Metal Catalysts