THESIS
2019
xv, 143 pages : illustrations ; 30 cm
Abstract
DFT studies on the reaction mechanisms for Cu(I)-catalyzed dearomatization of pyridine,
Pd(II)-catalyzed B-H bond activation of o-carborane, stoichiometric reactions of borylene with
different nucleophiles, and stoichiometric reactions of diborane(4) with different Lewis bases
are reported in this thesis. The detailed reaction mechanisms, selectivity and structure analysis
have been explored.
Chapter 1 gave a short introduction of DFT methods, background information on
dearomatization, and chemistry of o-carborane, borylene and diborane(4) compounds. Chapter
2 dealt with 1,4-dearomatization reactions of pyridine catalyzed by Cu(I) complexes. One-copper
catalyst system can 1,4-dearomatize pyridine through consecutive structural
rearrangement of the styrene-inserted species. The...[
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DFT studies on the reaction mechanisms for Cu(I)-catalyzed dearomatization of pyridine,
Pd(II)-catalyzed B-H bond activation of o-carborane, stoichiometric reactions of borylene with
different nucleophiles, and stoichiometric reactions of diborane(4) with different Lewis bases
are reported in this thesis. The detailed reaction mechanisms, selectivity and structure analysis
have been explored.
Chapter 1 gave a short introduction of DFT methods, background information on
dearomatization, and chemistry of o-carborane, borylene and diborane(4) compounds. Chapter
2 dealt with 1,4-dearomatization reactions of pyridine catalyzed by Cu(I) complexes. One-copper
catalyst system can 1,4-dearomatize pyridine through consecutive structural
rearrangement of the styrene-inserted species. The selectivity between 1,2- and 1,4-
dearomatization reactions was also explored. Chapter 3 studied selective functionalization of
o-carborane B(3)-H and B(4)-H bonds. The mechanisms of B(3)-H and B(4)-H acetoxylation
of o-carboranes catalyzed by Pd(II) complexes and B(3)-H and B(4)-H amination of 1-COOH-2-CH
3-C
2B
10H
10 catalyzed by Ir(III) and Rh(III) complexes were examined and discussed.
Chapter 4 was about the structure and bonding analysis of different three-coordinate borylenes
and mechanistic studies of borylene with 9-BBN and H
2. And the regioselectivity for the
reactions of borylene with different nucleophiles was also studied. In Chapter 5, the reactions
of tetra(o-tolyl)diborane(4) with different Lewis bases, such as isocyanides, cyanides,
pyridazine and phthalazine, have been carefully explored. The influence of the different
substituents on isocyanides and cyanides on the reaction outcomes was studied and addressed.
Activation of the N=N double bond in pyridazine or phthalazine was also calculated and
discussed. Finally, a short summary was given in Chapter 6.
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