THESIS
2021
1 online resource (xvii, 184 pages) : illustrations (some color)
Abstract
Theoretical studies on the reactivity of organoboron compounds, transition-metal boryl
complexes, and acyclic silylene have been reported with the aid of DFT calculations in this
thesis. We have unraveled reaction mechanisms based on experimental results and have made
useful predictions on some cases. For organoboron compounds, the reactivity is dependent on
the Lewis acidity of the empty p orbital of the boron center. Once the empty p orbital of the
boron center is occupied by a nucleophile, the remaining three bonds around the boron center
could be activated and undergo further migrations/transformations. This important insight helps
us understand phosphine-catalyzed trans-hydroboration of alkynoate esters (Chapter 2), the
reactivity of diborane compounds toward organic azides (Chapte...[
Read more ]
Theoretical studies on the reactivity of organoboron compounds, transition-metal boryl
complexes, and acyclic silylene have been reported with the aid of DFT calculations in this
thesis. We have unraveled reaction mechanisms based on experimental results and have made
useful predictions on some cases. For organoboron compounds, the reactivity is dependent on
the Lewis acidity of the empty p orbital of the boron center. Once the empty p orbital of the
boron center is occupied by a nucleophile, the remaining three bonds around the boron center
could be activated and undergo further migrations/transformations. This important insight helps
us understand phosphine-catalyzed trans-hydroboration of alkynoate esters (Chapter 2), the
reactivity of diborane compounds toward organic azides (Chapter 3), the reactivity of borole
compounds toward epoxides (Chapter 4), and the reactivity of borole cycloaddition reactions
(Chapter 5). For transition-metal boryl complexes, we have reported theoretical studies on the
reactivity of a (NHC)Au-diarylboryl toward polar multiple bond molecule (Chapter 6) and Rh-catalyzed
deoxygenative borylation of ketones (Chapter 7). Based on these studies and a series
of previous work of our group on the reactivity of (NHC)Cu-boryl complexes, we have
systematically compared the reactivities of different metal-boryl complexes toward phenyl
aldehyde (Chapter 8), and pointed out that in addition to that the metal-boryl σ-bonding
electrons could play the nucleophilic role, the electrophilicity of “empty” p orbital on the boron
center of a boryl ligand, and the nucleophilicity of d electron pairs of the metal center could
initiate a reaction as well. Apart from boron chemistry, theoretical studies on the reactivity of a
silylene compound toward small gas molecule (CO, CO
2 and N
2O) activation is also reported
(Chapter 9), our study has provided an in-depth understanding of the acyclic silylene’s single-site
ambiphilic reactivity.
Post a Comment