The theoretical calculations on a series of intramolecular α-hydrogen transfer reactions in organometallic rhenium complexes R³R⁵(NHR⁴)Re(＝CHR¹)(＝NR²) were carried out with B3LYP method and the effects of substituents on the barriers of the α-hydrogen transfer reactions were explored. It was found that the most preferable substituents are methyl or t-butyl groups for R¹ while the hydrogen atom is the best one for R². For R³ and R⁴, the most suitable groups are silyl and t-butyl groups, respectively. Calculation results also show that additivity exists for the effects of substituents on the barriers of the α-hydrogen transfer reactions.

Key words: organometallic rhenium complex, α-hydrogen transfer reaction, density functional theory