R. Kempe et al., ACTIVATION OF CO2 AT TRANSITION-METAL CENTERS - THE ROUTE OF THE CO2 REDUCTION AT NIKEL(0) MOIETIES, Zeitschrift fur anorganische und allgemeine Chemie, 619(6), 1993, pp. 1105-1110
Citations number
18
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Zeitschrift fur anorganische und allgemeine Chemie
A competing reaction in the catalytic cyclooligomerization of hex-3-yn
e and CO2 at the (TMED)Ni(0)-fragment (TMED = N,N,N',N'-tetramethyleth
ylendiamine) is the formation of carbon monoxide and (TMED)Ni(CO,). So
it is possible to explain the generation of II (TMED)Ni(diethylmalica
cidanhydride) and III (a nickel trimer with two (TMED)Ni(CO,) units).
Both complexes are characterized by X-ray analysis. The reduction of C
O2 to CO most likely proceeds via an intermediate in which two molecul
es of carbon dioxide are coupled head-to-tail to form a metallacycle.
An ab initio scf geometry optimization supports the existence of such
an intermediate.