New nickel–carbon dioxide complex: synthesis, properties, and crystallographic characterization of (carbon dioxide)-bis(tricyclohexylphosphine)nickel

Structurally simple complexes of CO2

“…The first structurally characterized complex of carbon dioxide bound to a transition metal was reported by Aresta et al in 1975. 10 These authors prepared [Ni(CO2)(PCy)3] · 0.75 C7H8 (Cy = cyclohexyl) and using X-ray crystallography showed the carbon dioxide to be coordinated to the nickel center in an η 2 -fashion, through the carbon and one oxygen atom of the markedly bent CO2.…”

Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide

“…In contrast to all these protocols, the use of abundant CO 2 is desirable. However, because of its thermodynamic and kinetic stability [18][19][20][21] , the catalytic C-C bond formation between carbon dioxide and olefins constitutes one of the most challenging tasks for organometallic chemistry. So far, the reported carboxylation of alkenes with carbon dioxide proceeds only in the presence of (over)stoichiometric amounts of strong or expensive reductants like Et 2 Zn and silanes [22][23][24] .…”

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

“…Surprisingly, scarce mechanistic studies have been reported on the coupling of alkenes and CO 2 in the presence of Ni(0) species. Experimentally, a pathway consisting of an oxidative cyclization from an Aresta-type CO 2 -coordinated Ni(0) complex [18] and an external alkene was ruled out, as the substitution of CO 2 by the olefin was rapidly observed [67,68]. This was also corroborated by the fact that nickelalactones decomposed at high temperatures to give the corresponding Ni(0)-olefin complexes by extrusion of CO 2 [47].…”

“…The direct carboxylation of organic compounds has traditionally been associated with the utilization of Ni complexes, an observation that can be traced back from the seminal work of Aresta and coworkers by the isolation of the first CO 2 complex to a transition metal [Ni(η 2 -CO 2 )(PCy 3 ) 2 ] [18]. In the last three decades, CO 2 fixation into unsaturated hydrocarbons has garnered considerable attention from the scientific community, either using stoichiometric or catalytic amounts of transition metals, reaching remarkable levels of sophistication, efficiency and applicability.…”