Journal article

Authors list: Geyer, C; Schindler, S

Publication year: 1998

Pages: 4400-4405

Journal: Organometallics

Volume number: 17

Issue number: 20

ISSN: 0276-7333

DOI Link: https://doi.org/10.1021/om980275b

Publisher: American Chemical Society

Abstract: 
The reactions of the nickel(0) complex [Ni(bipy)(COD)] (COD = cyclooctadiene, bipy = 2,2'-bipyridine) with isoprene (ip) in the absence and presence of carbon dioxide were investigated. A detailed kinetic analysis revealed that [Ni(bipy)(COD)] reacts reversible with ip and activation parameters for the forward and back reactions were calculated from a temperature dependence study to be the following: Delta H double dagger = 35 +/- 5 kJ/mol, Delta S double dagger = -79 +/- 16 J/(mol K) forward reaction (ip dependence); Delta H double dagger = 58 +/- 2 kJ/mol, Delta S double dagger = 58 +/- 10 J/(mol K) back-reaction (COD dependence at low temperatures). It could be shown that CO2 did not react with [Ni(bipy)(COD)] directly but with the nickel ip complex to form the product complex ((3-5-eta(3))-3-methyl-3-pentenylato)nickel bipyridine. The reaction proceeded in an associative way, during which CO2 was inserted into a Ni-C bond in an oxidative coupling step. The activation parameters mere calculated to be Delta H double dagger = 25 +/- 7 kJ/mol and Delta S double dagger = -184 +/- 24 J/(mol K).

Harvard Citation style: Geyer, C. and Schindler, S. (1998) Kinetic analysis of the reaction of isoprene with carbon dioxide and a nickel(0) complex, Organometallics, 17(20), pp. 4400-4405. https://doi.org/10.1021/om980275b

APA Citation style: Geyer, C., & Schindler, S. (1998). Kinetic analysis of the reaction of isoprene with carbon dioxide and a nickel(0) complex. Organometallics. 17(20), 4400-4405. https://doi.org/10.1021/om980275b