A Mechanistic Study of the Migratory Insertion Reaction: A Computational Chemistry Exercise

作者：Montgomery Craig D^*

来源：Journal of Chemical Education, 2013, 90(10): 1396-1400.

DOI：10.1021/ed300526k

• Upper-Division Undergraduate
• Inorganic Chemistry
• Laboratory Instruction
• Computer-Based Learning
• Hands-On Learning/Manipulatives
• Coordination Compounds
• IR Spectroscopy
• Mechanisms of Reactions
• Molecular Modeling Organometallics

An exercise in computational chemistry is presented whereby the student models the mechanism of migratory insertion. In the case of migratory insertion of CO into the Mn-CH3 bond of [Mn(CH3)(CO)(5)], semiempirical calculations (PM3) are used to evaluate the concerted mechanism of methyl migration, followed by coordination of CO. The three-centered transition state is determined along with the activation energy, calculated to be 131 kJ/mol. The 16-electron intermediate [Mn(C(O)CH3)(CO)(4)] is suggested to display an agostic Mn-H interaction as has been postulated previously. The exercise is appropriate as a take-home assignment in a course on inorganic or organometallic chemistry.

• 出版日期2013-10