Bond-shift rearrangement during hydrogenolysis of neopentyl iodide on group VIII metal catalysts. An analogue of the mechanism of action of vitamin B12

✍ Scribed by Valia Amir-Ebrahimi; John J. Rooney

• Publisher: Elsevier Science
• Year: 1997
• Tongue: English
• Weight: 323 KB
• Volume: 120
• Category: Article
• ISSN: 1381-1169
• DOI: 10.1016/s1381-1169(96)00436-0

✦ Synopsis

The hydrogenolysis of neopentyl iodide on reduced Co or Pt dispersed on MgO support yields increasing amounts of 2-metylbutane and 2-methylbutenes in addition to neopentane, as the temperature is raised from 50 to 150°C. These results support the idea that a n-complexed half-reaction state is simultaneously involved in activation of the R-I bond and in the evident 1,2-methyl shift. This n-complex mechanism is the same as that first suggested almost a quarter of a century ago for neopentane isomerism during hydrogenolysis at 3 200°C on F't catalysts. The present results also support the contention that similar n--complexes are responsible for analogous carbon skeleton rearrangement reactions mediated by coenzyme B ,2.