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Understanding the Structure, Bonding and Reactivity of Unsaturated Metallacycles : A Computational Study

Electronic Theses of Indian Institute of Science

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Title Understanding the Structure, Bonding and Reactivity of Unsaturated Metallacycles : A Computational Study
 
Creator Roy, Subhendu
 
Subject Metallacycles
Transition Metal Complexes
Metallacycloallenes
Titanium Metallacyclocumulenes
Zirconium Metallacyclocumulenes
Heterometallacycles
Metallocene-Alkyne Complexes
Metallacycles - Bonding
Metallacycles - Structure
Organometallic Compounds
Organometallic Chemistry
Metallocenes
Metallacyclopentynes
Metallacycloallene
Metallacyclocumulenes
Organic Chemistry
 
Description Stabilization of highly strained organic species and altering normal reactivity norms of organic fragments by transition metals have been a triumphing feat of organometallic chemistry. A variety of saturated and unsaturated metallacycles result from the reactions of the transition metals with the organic entities. Understanding the structure and bonding of the metallacylces has been indispensable over the years in view of its involvement as intermediates or compounds for numerous synthetic and catalytic applications. In this context, Group 4 metallocenes have unlocked a fascinating chemistry by stabilizing strained unsaturated C4 organic fragments in the form of five-membered metallacyclomulenes, metallacyclopentynes and metallacycloallnes. These molecules do not conform to the existing bonding principles of chemistry. We have carried out a comprehensive theoretical study to understand the unsual stability and reactivity of these metallacycles. Our theoretical study reveals that the unique interaction of the internal carbon atoms along with the terminal carbon atoms with the bent metallocene moiety is the reason for unsual stability of the metallacycles. We have also investigated the mechanism of interesting C-C coupling and cleavage reactions involving metallacyocumulenes. It demonstrates unexpected reaction pathway for these metallacycles. Moreover, based on this understanding, we have predicted and unraveled the stabilization factors of a challenging four membered metallcycloallene complex. Indeed, our prediction about a four-membered heterometallacycle has been realized experimentally. This kind of bonding is intriguing from fundamental perspective and has great relevance in synthesizing unsual structures with interesting properties. Finally, the electronic structure and bonding of a metallocene-alkyne complex is analyzed to determine the nature of bonding. Our aim is to build a conceptual framework to understand these metallacycles and to exploit their chemistry.
 
Contributor Jemmis, Eluvathingal D
 
Date 2018-04-05T03:31:44Z
2018-04-05T03:31:44Z
2018-04-05
2013
 
Type Thesis
 
Identifier http://etd.iisc.ernet.in/2005/3343
http://etd.iisc.ernet.in/abstracts/4208/G25737-Abs.pdf
 
Language en_US
 
Relation G25737