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GATE Chemistry 2024 ( Silicon Batch-3)
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Main Group Elements: Hydrides, halides, oxides, oxoacids, nitrides, sulfides – shapes and reactivity. Structure and bonding of boranes, carboranes, silicones, silicates, boron nitride, borazines and phosphazenes. Allotropes of carbon. Chemistry of noble gases, pseudohalogens, and interhalogen compounds. Acid-base concepts.
Transition Elements: Coordination chemistry – structure and isomerism, theories of bonding (VBT, CFT, and MOT). Energy level diagrams in various crystal fields, CFSE, applications of CFT, Jahn-Teller distortion. Electronic spectra of transition metal complexes: spectroscopic term symbols, selection rules, Orgel diagrams, charge-transfer spectra. Magnetic properties of transition metal complexes. Reaction mechanisms: kinetic and thermodynamic stability, substitution and redox reactions.
Lanthanides and Actinides: Recovery. Periodic properties, spectra and magnetic properties. Organometallics: 18-Electron rule; metal-alkyl, metal-carbonyl, metal-olefin and metal carbene complexes and metallocenes. Fluxionality in organometallic complexes. Types of organometallic reactions. Homogeneous catalysis - Hydrogenation, hydroformylation, acetic acid synthesis, metathesis and olefin oxidation. Heterogeneous catalysis - FischerTropsch reaction, Ziegler-Natta polymerization.
Radioactivity: Decay processes, half-life of radioactive elements, fission and fusion processes.
Bioinorganic Chemistry: Ion (Na+ and K+) transport, oxygen binding, transport and utilization, electron transfer reactions, nitrogen fixation, metalloenzymes containing magnesium, molybdenum, iron, cobalt, copper and zinc.
Solids: Crystal systems and lattices, Miller planes, crystal packing, crystal defects, Bragg’s law, ionic crystals, structures of AX, AX2, ABX3 type compounds, spinels, band theory, metals and semiconductors.
Instrumental Methods of Analysis: UV-visible spectrophotometry, NMR and ESR spectroscopy, mass spectrometry. Chromatography including GC and HPLC. Electroanalytical methods- polarography, cyclic voltammetry, ion-selective electrodes. Thermoanalytical methods.Stereochemistry: Chirality of organic molecules with or without chiral centres and determination of their absolute configurations. Relative stereochemistry in compounds having more than one stereogenic centre. Homotopic, enantiotopic and diastereotopic atoms, groups and faces. Stereoselective and stereospecific synthesis. Conformational analysis of acyclic and cyclic compounds. Geometrical isomerism. Configurational and conformational effects, and neighbouring group participation on reactivity and selectivity/specificity.
Reaction Mechanisms: Basic mechanistic concepts – kinetic versus thermodynamic control, Hammond’s postulate and Curtin-Hammett principle. Methods of determining reaction mechanisms through identification of products, intermediates and isotopic labeling. Nucleophilic and electrophilic substitution reactions (both aromatic and aliphatic). Addition reactions to carbon-carbon and carbon-heteroatom (N,O) multiple bonds. Elimination reactions. Reactive intermediates – carbocations, carbanions, carbenes, nitrenes, arynes and free radicals. Molecular rearrangements involving electron deficient atoms.
Organic Synthesis: Synthesis, reactions, mechanisms and selectivity involving the following classes of compounds – alkenes, alkynes, arenes, alcohols, phenols, aldehydes, ketones, carboxylic acids, esters, nitriles, halides, nitro compounds, amines and amides. Uses of Mg, Li, Cu, B, Zn and Si based reagents in organic synthesis. Carbon-carbon bond formation through coupling reactions - Heck, Suzuki, Stille and Sonogoshira. Concepts of multistep synthesis - retrosynthetic analysis, strategic disconnections, synthons and synthetic equivalents. Umpolung reactivity – formyl and acyl anion equivalents. Selectivity in organic synthesis – chemo-, regio- and stereoselectivity. Protection and deprotection of functional groups. Concepts of asymmetric synthesis – resolution (including enzymatic), desymmetrization and use of chiral auxilliaries. Carbon-carbon bond forming reactions through enolates (including boron enolates), enamines and silyl enol ethers. Michael addition reaction. Stereoselective addition to C=O groups (Cram and Felkin-Anh models).
Pericyclic Reactions and Photochemistry: Electrocyclic, cycloaddition and sigmatropic reactions. Orbital correlations - FMO and PMO treatments. Photochemistry of alkenes, arenes and carbonyl compounds. Photooxidation and photoreduction. Di-π-methane rearrangement, Barton reaction.
Heterocyclic Compounds: Structure, preparation, properties and reactions of furan, pyrrole, thiophene, pyridine, indole, quinoline and isoquinoline.
Biomolecules: Structure, properties and reactions of mono- and di-saccharides, physicochemical properties of amino acids, chemical synthesis of peptides, structural features of proteins, nucleic acids, steroids, terpenoids, carotenoids, and alkaloids.
Spectroscopy: Applications of UV-visible, IR, NMR and Mass spectrometry in the structural determination of organic molecules