Mechanism of co-dimerization of vinylboronates with terminal alkynes catalyzed by ruthenium-hydride complex

• Mechanism of co-dimerization reaction was reported by DFT calculations.
• Kinetic measurements were carried out to confirm the computational studies.
• BLYP, B3LYP, M06 functionals, LANL2DZ, SDD bases were employed in the DFT calculations.
• The rate-determining step of the process is the β-hydride elimination of the product.
• The activation energy, determined experimentally, is in agreement with the DFT studies.

The co-dimerization reaction of vinylboronates with terminal alkynes, which was discovered in our group, is an efficient method for the synthesis of boryl- and borylsilylsubstituted buta-1,3-dienes. This study is a continuation of our previous and present results concerning the mechanism of this new catalytic reaction in boron chemistry. DFT calculations, as well as kinetic measurements carried out at several different temperatures in the range of 70–100 °C, provided rational grounds for the mechanism proposed previously on basis of stoichiometric reactions monitored by 1H NMR. The activation energy and the rate determining step were also estimated.

Figure optionsDownload high-quality image (45 K)Download as PowerPoint slide