Kinetics and mechanism of the reaction of HCo(CO)4 with 2,3-dimethyl-1,3-butadiene

F. Ungváry, László Markó

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Abstract

Spectroscopic evidence and the kinetics of CO uptake in the reaction of HCo(CO)4 (1) with 2,3-dimethyl-1,3-butadiene (2) are consistent with a rate-determining concerted 1,4 addition of 1 to the s-cis conformation of 2 forming (2,3-dimethyl-2-butenyl)cobalt tetracarbonyl (3): k15°C = 1.42 × 10-2 M-1 s-1 (k15°C = 1.79 × 10-2 M-1 s-1 with DCo(CO)4). The intermediate 3 successively (a) rearranges in a first-order reaction to (3,4-dimethyl-3-pentenoyl)cobalt tricarbonyl (4), which in turn adds CO to form (3,4-dimethyl-3-pentenoyl)cobalt tetracarbonyl (5), and (b) reacts with 1 in a bimolecular homolytic displacement reaction leading to 2,3-dimethyl-1-butene where a H atom is abstracted from 1 by the γ-carbon atom of 3 and simultaneously ·Co(CO)4 is eliminated. The ratio of the rate constants of these two competing fast reactions is 20.7 M-1 (12.5 M-1 in the case with DCo(CO)4) at 5°C.

Original languageEnglish
Pages (from-to)1466-1470
Number of pages5
JournalOrganometallics
Volume3
Issue number10
Publication statusPublished - 1984

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Carbon Monoxide
butadiene
Kinetics
cobalt
kinetics
Cobalt
butenes
atoms
Atoms
Conformations
2,3-dimethyl-1,3-butadiene
carbon
Rate constants
Carbon

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Kinetics and mechanism of the reaction of HCo(CO)4 with 2,3-dimethyl-1,3-butadiene. / Ungváry, F.; Markó, László.

In: Organometallics, Vol. 3, No. 10, 1984, p. 1466-1470.

Research output: Contribution to journalArticle

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N2 - Spectroscopic evidence and the kinetics of CO uptake in the reaction of HCo(CO)4 (1) with 2,3-dimethyl-1,3-butadiene (2) are consistent with a rate-determining concerted 1,4 addition of 1 to the s-cis conformation of 2 forming (2,3-dimethyl-2-butenyl)cobalt tetracarbonyl (3): k15°C = 1.42 × 10-2 M-1 s-1 (k15°C = 1.79 × 10-2 M-1 s-1 with DCo(CO)4). The intermediate 3 successively (a) rearranges in a first-order reaction to (3,4-dimethyl-3-pentenoyl)cobalt tricarbonyl (4), which in turn adds CO to form (3,4-dimethyl-3-pentenoyl)cobalt tetracarbonyl (5), and (b) reacts with 1 in a bimolecular homolytic displacement reaction leading to 2,3-dimethyl-1-butene where a H atom is abstracted from 1 by the γ-carbon atom of 3 and simultaneously ·Co(CO)4 is eliminated. The ratio of the rate constants of these two competing fast reactions is 20.7 M-1 (12.5 M-1 in the case with DCo(CO)4) at 5°C.

AB - Spectroscopic evidence and the kinetics of CO uptake in the reaction of HCo(CO)4 (1) with 2,3-dimethyl-1,3-butadiene (2) are consistent with a rate-determining concerted 1,4 addition of 1 to the s-cis conformation of 2 forming (2,3-dimethyl-2-butenyl)cobalt tetracarbonyl (3): k15°C = 1.42 × 10-2 M-1 s-1 (k15°C = 1.79 × 10-2 M-1 s-1 with DCo(CO)4). The intermediate 3 successively (a) rearranges in a first-order reaction to (3,4-dimethyl-3-pentenoyl)cobalt tricarbonyl (4), which in turn adds CO to form (3,4-dimethyl-3-pentenoyl)cobalt tetracarbonyl (5), and (b) reacts with 1 in a bimolecular homolytic displacement reaction leading to 2,3-dimethyl-1-butene where a H atom is abstracted from 1 by the γ-carbon atom of 3 and simultaneously ·Co(CO)4 is eliminated. The ratio of the rate constants of these two competing fast reactions is 20.7 M-1 (12.5 M-1 in the case with DCo(CO)4) at 5°C.

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