CHEM20170 Intermediate Inorganic & Materials Chemistry

Unit catalogue DLM

Chemical Applications of Group Theory

Lecturer Dr Colin Western
Format 8 lectures
Learning objectives
  • Understand the basic terminology and notation used to describe the symmetry of molecules
  • To be able to determine the point group of a molecule
  • To be able to determine the symmetry (irreducible representation) of molecular properties such as vibrations and molecular orbitals
  • To be able to use symmetry to predict molecular behaviour such as allowed transitions
Synopsis This course will teach the basic ideas, methods and notation of group theory as used in Chemistry. It will provide essential underpinning for subsequent second-year courses and beyond in Inorganic, Physical and Theoretical Chemistry where the methods and notation are used and will provide a framework for understanding research literature where ideas from group theory are encountered. The emphasis will be very much on using the tools and notation for chemical problems, rather than deriving the underlying theory. Topics covered will include
  • Symmetry elements (rotation, reflection, centre of symmetry, improper rotations)
  • Point groups and how to work them out for simple molecules
  • Character tables, characters, degeneracy and irreducible representations
  • Vibrations in molecules (mainly stretching vibrations), their symmetry and how to determine their infrared and Raman activity
  • Construction of molecular orbitals for simple polyatomic molecules such as H2O, CH4, SF6 Additional selected applications to link with other courses including bonding in octahedral complexes and using programs (such as Gaussian) to calculate molecular orbitals
Additional reading
  • Molecular Symmetry and Group Theory, 2nd Edition, A. Vincent, Wiley, 2001
The required material on group theory is also covered in many general inorganic and physical textbooks, though note that some give more mathematical detail than is required for this course.

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Coordination Chemistry

Lecturer Dr Chris Russell
Format 8 lectures
Learning objectives
  • The explanation of the spectrochemical series using Molecular Orbital theory
  • An understanding of the word stability in coordination complexes and how to assess this quantitatively
  • The types of inorganic reaction mechanisms
  • The application of the trans influence and trans effect
  • The effects of d electron counts on the kinetic and thermodynamic stability of complexes
Synopsis This course will build on the first-year Chemistry for Life Sciences Transition Metal Chemistry course and will use elements from the second-year Group Theory course. Connections will be made to other second-year courses in Organometallic Chemistry and Main Group Chemistry. It will lay the foundation for third-year and fourth-year courses in coordination chemistry, bioinorganic chemistry and medicinal inorganic chemistry. Topics covered will include:
  • The scope and importance of coordination chemistry (s-, p-, d-, f-block, applications from biomedical to materials)
  • A review of concepts from first year including oxidation state, dn number, coordination geometries, crystal field splittings
  • Hard and soft acids and bases
  • Deficiencies in Crystal Field Theory leading to Ligand Field Theory (based on Group Theory approach)
  • The thermodynamics of complexation including electrode potentials
  • The kinetics of complexation; determination of A, D and I mechanisms; factors affecting rates of water exchange in [M(OH2)6]n+; Jahn-Teller effects
  • Substitution in square planar complexes; trans effect and trans influence;substitution in octahedral complexes
  • Electron-transfer mechanisms (inner sphere/outer sphere); Frank-Condon Principle
Additional reading
  • J. R. Gispert, Coordination Chemistry, VCH, 2008
  • Transition Metal Chemistry, M Gerloch and EC Constable, VCH, 1994
  • Inorganic Chemistry, 4th Edition, CE Housecroft and AG Sharpe, Pearson, 2012
  • Chemistry of the Elements, 2nd Edition, NN Greenwood and A Earnshaw, Butterworth-Heinemann, 1997
  • d-Block Chemistry, MJ Winter, Oxford Chemistry Primer, 1994
  • Chemistry of the First Row Transition Metals, JA McCleverty, Oxford Chemistry Primer, 1999
  • The Mechanisms of Reactions at Transition Metal Sites, RA Henderson, Oxford Chemistry Primer, 1993
  • Inorganic Reaction Mechanisms, ML Tobe and J Burgess, Longman, 1999

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Main Group Chemistry

Lecturer Professor Nick Norman
Format 8 lectures
Learning objectives
  • An understanding of the concepts of shielding, effective nuclear charge, atomic radii, ionisation energies, electron affinities and electronegativity
  • An understanding of the concepts of closed shell configurations, oxidation states, inert pair effect, stability of multiple bonds, strength of single bonds, catenation
  • An understanding of periodicity and the structure of the periodic table
  • An understanding of the various types of multicentre bonding, importance of d-orbitals and σ*-orbitals, and Wade‘s Rules
  • A basic knowledge of the chemistry of hydrides, halides and oxides including acidity, basicity and amphoterism
  • A basic knowledge of the preparation and properties of selected main group polymers
Synopsis This course will build on the first-year Introductory Chemistry Molecules course and, in particular, on the first-year Chemistry for Physical Scientists, Main Group Chemistry course. It will also use elements from the second-year Group Theory and NMR Spectroscopy courses and it will lay the foundations for second-year and fourth-year courses that cover main group chemistry. Topics covered will include:
  • An initial review and revision of concepts from first-year lectures (primarily, the Chemistry for Physical Scientists, Main Group Chemistry course) including: shielding, effective nuclear charge, atomic radii, ionisation energies and electron affinities, and electronegativity
  • A review of other general points including:
    • Closed shell configurations
    • The distribution in the Periodic Table of metals, non-metals and metalloids (with definitions of each)
    • Oxidation states including high oxidation states, the inert pair effect, and group maximum oxidation states for the 4p elements
    • Bond energies (including homonuclear, heteronuclear and multiple) and atomic size effects
  • Trends in and general features of the structures of the p-block elements
  • An overview of selected compounds of the p-block elements including:
    • General features with an emphasis of structure, bonding and reactivity
    • Illustrative examples of chlorides and oxides
    • Acidic, basic and amphoteric oxides
  • Selected topics including:
    • Xenon chemistry
    • Bonding and orbitals including 3c, 2e bonds in diborane and 3c, 4e bonds in XeF2, d-orbitals and σ*-orbitals
    • Boranes and other main group clusters and Wade’s rules
    • Main group polymers including silicones, phosphazenes, sulfur-nitrogen compounds and boron-nitrogen compounds
Additional reading Periodicity and the s- and p-Block Elements, N C Norman, Oxford Chemistry Primer, 1997

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Materials Chemistry

Lecturer Dr Simon Hall
Format 8 lectures
Learning objectives
  • An understanding of the concepts of metallic bonding and alloy formation
  • An understanding of superconductivity
  • An understanding of defects in crystals and concomitant conductivity
  • A basic knowledge of how materials fail
  • An understanding of materials and processes used in nuclear weapons
Synopsis This course will build on the first-year Chemistry for Physical Scientists Materials course. Connections will be made to the other second-year courses Main Group Chemistry and Interfaces, Energy Conversion and New Materials. It will lay the foundation for third-year and fourth-year courses in advanced functional materials, bio-inorganic chemistry, the chemistry of solids and f-block chemistry. Topics covered will include:
  • Metallic bonding and alloy composition
  • Complex crystals; defects, radiation damage, colour centres and conductivity
  • Magnetic materials; hard and soft magnets and domain structures
  • Materials for nuclear applications; construction of fission and fusion devices
  • The chemistry and physics of the superconducting state
  • Nanotoxicology; nanotechnology – challenges and fears, how to detect nanoparticles
  • Failure modes in materials including brittle and ductile fractures and corrosion
Additional reading
  • Introduction to Solid State Physics, 8th Edition,C Kittel, Wiley, 2005
  • The Physics and Chemistry of Solids, SR Elliott, Wiley, 1998
  • Inorganic Materials Chemistry, MT Weller, Oxford Chemistry Primer, 1994
  • The Making of the Atomic Bomb, R Rhodes, Simon & Schuster, 1988
  • Dark Sun: the Making of the Hydrogen Bomb, R Rhodes, Simon & Schuster, 1995

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NMR Spectroscopy

Lecturer Dr Craig Butts
Format 8 lectures
Learning objectives
  • To recall fundamentals of NMR from first-year Introductory Chemistry Characterisation course
  • To understand the way in which signals are related to chemical structures through symmetry/equivalence
  • To understand how chemical shift and coupling constants can be related to chemical structures
  • To recognise the effects of coupling in heteronuclear systems
  • To understand the impact of chemical/structural dynamics on NMR spectra
  • To understand the nature of, and couplings to, non I = ½ nuclei
  • To understand the basis of solid-state NMR spectroscopy as compared to solution-state methods
  • To understand the basis of electron spin resonance spectroscopy and relationships to NMR spectroscopy
Synopsis This course will build on the brief (2 lecture) introduction to NMR spectroscopy in the first-year Introductory Chemistry Characterisation lectures. Connections will be made to other second-year courses in the Inorganic and Materials and Organic and Biological units. The course will begin with a review of Introductory Chemistry material and basic principles and then cover in more detail the nuclear spin quantum number, a survey of NMR-active (especially I= ½) nuclei in the periodic table, the resonance condition, diamagnetic screening, chemical shift, integration, and spin-spin coupling. NMR of specific nuclei will then be covered in more detail. Topics covered will include:
  • 13C NMR: A review of nuclear properties, relative sensitivity, TMS reference, typical chemical shift ranges
  • 13C NMR: Broad band 1H decoupling and signal intensities (NOE effect)
  • 1H NMR: A review of equivalence, characteristic chemical shifts for protons and the basis of spin-spin coupling
  • 1H NMR: Further factors affecting chemical shifts of protons including ring currents and screening cones, NMR timescale, “free” (ethane) bond rotation, coupling constants and 3JHH, factors affecting the magnitude of coupling constants 1J, 2J, 3J, 4J and 5J, angular dependence of 3J (mention of Karplus), distinguishing cis and trans alkenes, second order distortions (AB)
  • 19F and 31P NMR: Some applications of 19F NMR in main group chemistry, applications of 31P NMR in coordination chemistry and coupling to 103Rh and 195Pt
  • Dynamic processes: Intermolecular (phosphine exchange), and intramolecular (restricted rotation in amides and pseudorotation in PF5)
  • Coupling of protons to other I = ½ nuclei (31P, 19F,103Rh), satellites with 13C, 195Pt, 117,119Sn, metal alkyls, metal hydrides, effects on spectra of intermolecular proton exchange (eg EtOH), choice of solvents, and the TMS reference
  • Non-I = ½half; nuclei (11B, 10B, 2H) and coupling to these nuclei from I = ½half; nuclei (31P, 19F, 1H, 13C)
  • Introduction to solid-state NMR spectroscopy: 13C and 29Si, dipolar coupling, magic-angle spinning
  • Introduction to Electron Spin Resonance (ESR) spectroscopy: g-factors, hyperfine coupling and lineshape
Additional reading
  • Introduction to Organic Spectroscopy, L M Harwood and T D W Claridge, Oxford Chemistry Primer, 1997
  • Organic Spectroscopy, 3rd Edition, W Kemp, Macmillan, 1991
  • NMR in Chemistry – a Multinuclear Introduction, W Kemp, Macmillan, 1986

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Organometallic Chemistry and Catalysis

Lecturer Professor Paul Pringle
Format 8 lectures
Learning objectives
  • An understanding of the σ-, Π- and δ-bonding of organic fragments to metals.
  • A basic knowledge of the fundamental reactions of transition metal organometallic compounds
  • An understanding of the steps in simple catalytic cycles 
Synopsis

This course will build on the first-year Chemistry for Life Sciences Transition Metal Chemistry course. Connections will be made to other second-year courses in Coordination Chemistry and Main Group Chemistry. It will lay the foundation for the third-year courses in organometallic chemistry and homogeneous catalysis (across inorganic and organic chemistry). Topics covered will include:

  • The scope and importance of organometallic chemistry (s-, p-, d-, f-block and catalysis applications from organic synthesis to commodity chemicals manufacture)
  • A review of concepts from first-year including metal carbonyls, the 18 e− rule, the 16 e− rule for d8 complexes
  • Bonding of metals to alkenes, dienes, alkynes, cyclopentadienyls, arenes and phosphorus(III) ligands
  • Activation of coordinated alkenes to nucleophilic / electrophilic attack
  • Oxidative addition (eg H2, MeI) and reductive elimination (eg RH, RCOX)
  • Migratory insertions (alkene into M-H, CO into M-alkyl) and β-hydrogen elimination
  • The mechanism of alkene isomerisation and hydrogenation catalysis
  • The mechanism of methanol carbonylation 
Additional reading
  • Organometallics 1 and 2, M Bochmann, Oxford Chemistry Primers, 1994
  • The Organometallic Chemistry of the Transition Elements, 5th Edition, RH Crabtree, Wiley, 2009
  • Organometallics and Catalysis, M. Bochmann, Oxford University Press, 2015.

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