Unusual catalysis with nickel(0) complexes

Abstract

Suwwzznvy Several nickel( 0) complexes are excellent substrates containing carbon-halogen bonds,l cnrboncatalysts for the formation of alkylene carbonates from carbon n-bonds,2 and strained o-bonds," there are few data alkylene oxides and carbon dioxide.describing similar catalysis with compounds containiiig carboli-ox ygen bonds. SOLUBLE low-valent transition metal complexes have beenWe report that a series of co-ordinatively unsaturated recognized as important agents for effecting stoicheiornetric zerovalcnt nickel coillplexes catalyse the formation of and catalytic traiisforniations of various organic sub-alliylene carbonates: from certain eposides and carbon strates. U'hile nunierous catalytic reactions have been dioxide. %lien epoxyethme and carbon dioxide are hc-ated reported involving transition-metal-activation of organic at 100" in benzene solution containing L,Si5 (I, = Ph,I'), t Current address, PCR, Inc., Gaiiiesville, Florida 32G01.$ All inorganic complexes were satisfactorily characterized by elemental analyses, inolecuIar wieght determinations, and i.r. and n.m.r. spectroscopy while the organic carboiiates gave mass, i.r., and n.m.r. spectra consistent with their structures.

Theoretical study on the mechanism of nickel(0)-mediated coupling between carbon dioxide and epoxyethane

“…However, most catalysts, such as metalhalides [14,15], metal oxides [16,17], organometallic compounds [18][19][20], Lewis acid/bases [21], and zeolites [22], suffer from low catalytic activity or need harsh reaction conditions (high pressures of CO 2 and high temperatures), limiting their practicality. Some of these obstacles have been overcome with the development of metal (nickel, palladium, or platinum) complexes [28][29][30] that mediate the oxidative coupling of CO 2 with various epoxides. Among these transition metals, Ni appears great promise due to its inexpensiveness.…”

Carbon Dioxide Fixation into Organic Compounds

“…Organometallic halides RnMX m or RnMXm/Base [33], where R-Me, Et, Bu, Ph; M-Sn, Te, Sb, Bi, Ge, Si; X-Cl, Br, I, are good catalysts. Classical Lewis acids , organometallic complexes, e.g., (Phl)2Ni [34], heteropolyacids and metal phtalocyanines [35] (M = Co, Cr, Fe, Mn) have also been used as catalysts for reaction (6). Most recently, metal oxides (MgO [36], MgO/Ah03 [37], Nb 20s [38], others) have been used as heterogeneous catalysts.…”

Nickel-catalyzed electrochemical carboxylation of epoxides: mechanistic aspects

“…7 Recently, such metallacycles have been prepared and characterized from Ni(COD) 2 in the presence of N-donor ligands such as 2,2'-bipyridine or TMEDA 14 (Scheme 1).…”