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Exploring Structure and Reactions : Computational Studies on Three-Membered Rings, Metal-Boron Multiple Bonds and Biradical Reactions

Electronic Theses of Indian Institute of Science

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Title Exploring Structure and Reactions : Computational Studies on Three-Membered Rings, Metal-Boron Multiple Bonds and Biradical Reactions
 
Creator Mallick, Dibyendu
 
Subject Biradical Reactions
Ring Chemistry
Cyclic Isomers - Electronic Structure
Cyclization (Chemistry)
Ring Formation (Chemistry)
Metal-Borone Multiple Bonds
Cyclic Isomers - Bonding
Three-membered Boron Hydrides
Three-membered Aluminium Hydrides
Neutral Planar Rings
Three-Membered Ring Chemistry
Molecules - Structure and Bonding
Myers-Saito Cyclization
Garratt-Braverman Cyclization
Myers-Saito Cyclization
Inorganic Chemistry
 
Description The utility of computational study lies not only in rationalizing a chemical phenomenon but also in its predictive value. Broadly, the scope of my research work includes understanding of the structure and bonding of
molecules as well as reaction mechanisms using computational techniques.
Here I will discuss three research problems where computational results successfully rationalize and predict the experimental outcome.
Firstly, we will describe the electronic structure and bonding of all the
possible cyclic isomers of B2AlHnm (where n =3D 3 =96 6 and m =3D -2 to 1) =
which is isoelectronic to the cyclopropenyl cation.1 A comparative study among
all the isomers of homocyclic and heterocyclic three- membered boron and
aluminum hydrides has also been done to understand the factors that differentiate their hydride chemistry. We will also discuss about two different approaches to stabilize neutral planar B3R3 rings. In a
mechanistic study, we have designed a a priori system which can undergo two competing biradical generating processes, namely the Myers-Saito (MS) and Garratt-Braverman (GB) Cyclizations.2,3 We will present a detailed
mechanistic study of both the reactions, which indicates the preference of the GB cyclization over MS cyclization. The theoretical prediction is in agreement with the experimental findings. We will also describe a conformational constraint-based strategy to switch the selectivity from GB
to MS/Schmittel pathway.4 In another study, we will talk about a DFT study to illustrate the effect of the a) solvent, b) ancillary ligand, (L) c) leaving group, (Hal) and d) metal (M) on the equilibrium between metal
boryl (1) and borylene (2) complexes (Scheme 1).5,6
 
Contributor Jemmis, E D
 
Date 2018-04-06T05:58:01Z
2018-04-06T05:58:01Z
2018-04-06
2013
 
Type Thesis
 
Identifier http://etd.iisc.ernet.in/2005/3355
http://etd.iisc.ernet.in/abstracts/4222/G25753-Abs.pdf
 
Language en_US
 
Relation G25753