Journal article

Authors list: Geyer, C; Dinjus, E; Schindler, S

Publication year: 1998

Pages: 98-103

Journal: Organometallics

Volume number: 17

Issue number: 1

ISSN: 0276-7333

DOI Link: https://doi.org/10.1021/om970584m

Publisher: American Chemical Society

Abstract: 
The reactions of the nickel(0) complex [Ni(bipy)(COD)] (COD = cyclooctadiene, bipy = 2,2'-bipyridine) with benzaldehyde, propionaldehyde, and carbon dioxide/propionaldehyde were investigated. A detailed kinetic analysis revealed that [Ni(bipy)(COD)] reacts reversible with aldehydes and activation parameters for the forward and back reactions were calculated from a temperature dependence study: forward reaction (benzaldehyde) Delta H double dagger = 47.8 +/- 0.4 kJ/mol, Delta S double dagger = -47 +/- 1 J/(mol K); back reaction (COD) Delta H double dagger = 45 +/- 6 kJ/mol, Delta S double dagger = -61 +/- 19 J/(mol K) and forward reaction (propionaldehyde) Delta H double dagger = 55 +/- 3 kJ/mol, Delta S double dagger = -58 +/- 9.0 J/(mol K); back reaction (COD) Delta H double dagger = 39 +/- 0.5 kJ/mol, Delta S double dagger = -58 +/- 2 J/(mol K). It could be shown that carbon dioxide did not react with [Ni(bipy)(COD)] directly but with the nickel propionaldehyde complex to form a five-membered cyclic nickel complex. The reaction proceeded according to an associative mechanism, during which the carbon dioxide was inserted into a Ni-O bond by an oxidative coupling step. The activation parameters for this process were Delta H double dagger = 43 +/- 6 kJ/mol and Delta S double dagger = -129 +/- 19 J/(mol K).

Harvard Citation style: Geyer, C., Dinjus, E. and Schindler, S. (1998) Reactions of aldehydes with carbon dioxide at nickel(0) centers. A detailed kinetic analysis, Organometallics, 17(1), pp. 98-103. https://doi.org/10.1021/om970584m

APA Citation style: Geyer, C., Dinjus, E., & Schindler, S. (1998). Reactions of aldehydes with carbon dioxide at nickel(0) centers. A detailed kinetic analysis. Organometallics. 17(1), 98-103. https://doi.org/10.1021/om970584m