Chemistry/Geology-4
Class Head: Dr. D. Stirling
Class Handbook & Course Documentation
Chemistry/Geology -4H
Chemistry Component
Course Head: Dr Diane Stirling
Course Secretary: Miss Elizabeth McLean
CONTENTS PAGE
Timetable 3
General information 4
Booklist 5
Aims & objectives of courses 8
POLICY ON SUMMATIVE ASSESSMENT
All feedback on coursework used in assessment, including mid-year class exam/class test marks and
laboratory grades, is strictly provisional for your guidance only, and is subject to ratification by the
Board of Examiners and external examiners at the end of the academic year. You must retain all
copies of assessed work (lab notebooks, exam scripts, etc.) and have them available for inspection by
the examiners if requested at the end of the year. (You will be given reasonable advance warning
should this be required.)
GENERAL INFORMATION:CHEMISTRY/GEOLOGY-4H SESSION 1996-97
The Class Head is Dr Diane Stirling. In the event of illness or other reasons for absence, Dr Stirling
should be notified as soon as possible and, if appropriate, a relevant medical certificate should be
handed in to Mrs E Hughes Room A4-04.
LECTURE COURSES
Compulsory Lecture Courses: The five compulsory courses are listed in the timetable. They are given
during weeks 1 -8.
Option Courses: You must attend three option courses. You can choose any three from the list of
seven shown in the timetable. The courses on offer cover a wide range of topical subjects in modern
chemistry.
All courses consist of eight lectures. They will be given in the Physical Lecture Theatre.
TUTORIALS
Inorganic: Term 2: No formal tutorials. Students have a problem book. All inorganic staff will
post office hours.
Physical: Term 1: Weeks 2-10 Wednesdays at 4 pm in the Organic Lecture Theatre.
CLASS CERTIFICATES
You need to obtain a class certificate before you can sit the final degree examinations. To be certain of
a class certificate you must:
regularly attend lectures and tutorials, and appropriate courses, project and field work in
Geology (see Geology class handbook).
EXAMINATIONS
The Chemistry component of the degree examinations consist of three written papers. There is also a
third year carry-over mark.
All students must be available for oral examination by the external examiners on Tuesday, 17th June,
1997. This is an integral part of the degree examination.
CAREERS TALK AND DISCUSSION
Monday 29th October 1pm Organic Lecture Theatre.
Dr N Winterton, ICI, "To do or not to do a PhD", followed by open ended discussion.
Professor Winfield and Dr Muir will arrange individual interviews for all students early in Term 1 to
discuss their choices of a future career.
LECTURES
Alchemist Club and local R.S.C. meetings: Attendance at these talks, which are held on Thursdays at
4 pm, and at the Irvine Review Lectures is recommended and encouraged.
Irvine Review Lectures: St. Andrews, Friday 25th April, 1997. The subject is Pharmaceutical
Chemistry.
CHEM-3H & CHEM-4H: RECOMMENDED TEXTBOOKS FOR SESSION 1996-97
MOLECULAR MODELS: It is essential that all students possess a set of molecular models.
Orbit Molecular Building System: Organic and Inorganic Chemistry Individual Set, Cochrane,
£10.75. (Approx)
INORGANIC CHEMISTRY: It is essential that all students have a copy of:
Inorganic Chemistry, Second Edition, D F Shriver, P W Atkins and C H Langford, Oxford University
Press, 1994, £19.50.
The following three books are strongly recommended for purchase:
Basic Solid State Chemistry, A R West,John Wiley, £18.50.
Structural Methods in Inorganic Chemistry, Second Edition, E A V Ebsworth, D W H Rankin and S
Craddock, Blackwell, £19.95.
Particularly useful for laboratory and tutorial work and helpful in problem solving.
The Mechanisms of Reactions at Transition Metal Sites, R A Henderson, Oxford Science
Publications, £4.99.
PHYSICAL CHEMISTRY: It is essential that all students have a copy of:
Physical Chemistry, Second Edition, R A Alberty and R J Silbey, John Wiley, £21.00.
NOTE: ALL PRICES ARE SUBJECT TO CHANGE BY PUBLISHERS AT ANY TIME.
REFERENCE BOOKS HELD IN THE CHEMISTRY BRANCH LIBRARY
INORGANIC CHEMISTRY
Advanced Inorganic Chemistry, Fifth Edition, F A Cotton and G Wilkinson, John Wiley, £26.50.
Chemistry of the Elements, N N Greenwood and A Earnshaw, Pergamon, £29.00.
More of a reference book than a textbook, but contains factual information, particularly for main
group elements, which is more complete than in Cotton and Wilkinson.
Some Thermodynamic Aspects of Inorganic Chemistry, Second Edition, D A Johnson, Cambridge
U.P., £37.50. (Out of Print)
Inorganic Chemistry, Third Edition, A G Sharpe, Longman, £19.99.
Orbitals, Terms and States, M Gerloch, John Wiley, out of print.
A small book which should help to classify difficulties in understanding the nature of orbitals, terms
and states. Relevant to many courses in Inorganic and Physical Chemistry.
The Elements, Their Origin, Abundance and Distribution, P A Cox, O.U.P., £11.95.
Useful background and revision materials for Radiochemistry courses.
A Guide to Modern Inorganic Chemistry, S M Owen and A T Brooker, Longman, £12.99.
Sets out to answer the questions that are asked most often by students. A revision aid.
Heterogeneous Catalysis. Principles and Applications, G C Bond, O.U.P. £ not known.
PHYSICAL CHEMISTRY
Chemical Applications of Group Theory, Third Edition, F A Cotton, £61.00.
Group Theory for Chemists, G Davidson, Macmillan, £19.50, (Out of print).
Tables for Group Theory, P W Atkins, M S Child and C S G Phillips, O.U.P., £4.95.
Molecular Quantum Mechanics, Second Edition, P W Atkins, O.U.P., £23.50.
Modern Spectroscopy, Second Edition, J M Hollas, John Wiley, £16.95.
Fundamentals of Molecular Spectroscopy, Fourth Edition, C N Banwell, McGraw-Hill, £14.95.
Crystal Structure Analysis: a Primer, Second Edition, J P Glusker and K N Trueblood, O.U.P.,
£23.50.
Symmetry and Structure, S F A Kettle, John Wiley, £15.95.
Biophysical Chemistry, C R Cantor and P R Schimmel, W H Freeman & Co. £33.95.
Physical Chemistry, Fourth Edition, P W Atkins, OUP, £24.00.
Principles of Colloid and Surface Chemistry, Second Edition, P C Hiemenz, Marcel Dekker Inc.,
Colloid Science, D H Everett, Royal Society of Chemistry. £70.00.
Introduction to Colloid and Surface Chemistry, Fourth Edition, D J Shaw, Butterworth, Heinemann,
£14.95.
Title: Molecular Spectroscopy
Lecturer(s): Dr J K Tyler
Aims: This course aims to cover the fundamentals of molecular spectroscopy and to show how
details of molecular structure can be deduced from the study of rotational, vibrational and electronic
spectra of molecules.
Objectives:
After this course the student should understand the basic principles underlying the following
topics:
1. Energy changes and spectroscopic transitions. Units of spectroscopic measurements.
2. The Born-Oppenheimer approximation. The Boltzmann distribution and the population of
molecular energy states.
3. The basis of selection rules. Spontaneous and stimulated transitions. Spectral line shapes.
The principles of laser action.
4. Rotational spectra of molecules in the microwave and far-infrared regions.
5. Vibrational spectra of molecules in the infrared region.
6. Rotational and vibrational Raman spectroscopy.
7. The elucidation of detailed molecular structures from spectroscopic measurements.
Outline:
Molecular energy changes and molecular spectra. Spectroscopic units. The Born Oppenheimer
approximation and molecular motions. The Electromagnetic Spectrum. The interaction of e.m.
radiation and matter. Einstein A and B coefficients. The Boltzmann distribution. Spectroscopic
selection rules. Principles of laser action.
Rotational angular momenta and energy levels. Classification of molecular rotors through principal
moments of inertia. Details of selection rules and resulting spectra. Effects of applied electric fields -
the Stark effect. The determination of electric dipole moments. Molecular structure elucidation.
Practical considerations.
Vibrational spectra in the infrared region. The harmonic and anharmonic models for the diatomic
molecule. The Morse potential. Polyatomic molecules and normal modes of vibration. Group
frequencies. Rotational fine structures in molecular vibration spectra. Experimental aspects.
Light scattering and Raman specroscopy. Rayleigh and Raman scattering. Virtual states, polarisability
and selection rules. Pure rotational and vibrational-rotational Raman spectra. Polarisation of Raman
transitions.
Title: Surface Science
Lecturer(s): Dr M Kadodwala
Aims: To serve as an introduction into surface science, to describe modern spectroscopic techniques
of surface analysis ans how they can be applied to model systems.
Objectives:
1. Understand why UHV techniques are necessary to study model systems.
2. Be fluent in the nomenclature of surface structure and to understand concepts such as surface
relaxation and reconstruction.
3. Understand low energy electron diffraction and how it can be applied in the determination of
surface structure.
4. Understand adsorption at surfaces, and the importance of physisorption and chemisorption.
5. Knoe why electron based spectroscopic techniques are employed in surface science and be
familiar with those commonly used.
6. Understand the technique of temperature programmed desorption and its kinetics.
7. Know about vibrational spectroscopy at surfaces and their selection rules.
Outline:
What is surface Science ?
Ultra high vacuum, single crystal surfaces, surface density.
Techniques generally, electron surface sensitivity.
Electron spectroscopy:
Energy distribution curves
Auger electron spectroscopy
X-ray photoelectron spectroscopy (chemical shifts, relaxation)
UV photoelectron spectroscopy.
General adsorption:
Physisorption
Chemisorption
Sticking probability
Langmuir and precursor state adsorption
Accommodation.
Thermal desorption spectroscopy:
Kinetics of desorption.
Surface Structure:
Nomenclature
2D Bravais latticies
Relaxation
Low Energy electron diffraction (LEED):
Electron diffraction
Ewald sphere construction.
Reconstruction
Matrix notation.
Vibrations at surfaces:
RAIRS, HREELS, SERS, SFG
Selection rules
Vibrational relaxation.
Title: Main Group Organometallics
Lecturer(s): Dr R J Cross
Aims: To extend the knowledge of students in organometallic chemistry
Objectives:
1. Know about structures, bonding types and fluxionality in cyclopentadienyls of main group
elements.
2. Understand the relationship between structures of cyclopentadienyls and their physical and
chemical characteristics, including polarity, reactivity and solvation.
3. Know about and understand the reasons for the similarities and differences between these
compounds and (i) cyclopentadienyl transition metal compound and (ii) other main group
organometallics, including electron deficient molecules.
4. Understand how NMR spectroscopy and other physical and chemical techniques can be used
to elucidate the nature and structures of the above compounds, and be able to apply this understanding
to compounds not previously encountered.
5. Know the types and uses of organotin compounds; know how 119Sn NMR and Mössbauer
spectroscopy can be used to deduce structures.
6. Non-quantitative understanding of how the Mössbauer effect can be used, and of what
problems it can be applied to.
7. Understand the structure correlation method for relating static structures to dynamic
processes; know how this has been applied to 5-coordinate tin and zinc compounds, and related to
reaction pathways for tetrahedral substitution reactions.
8. Know the chemical nature and structure types of organo-arsenic, -antimony and -bismuth
compounds.
9. Non-quantitative understandingof how n.q.r. and e.s.r. spectroscopy can be applied to
structural and bonding problems of main group compounds.
Outline:
Trends and relationships in main group element cyclopentadienyl chemistry; structures, bonding and
fluxionality related to physical and chemical characteristics; tin organometallics; types, structures,
uses; applications of physical and spectro-scopic methods to elucidate natures and structures of
compounds; M"ssbauer spectroscopy; qualitative approach applied to 119Sn and 121Sn; structure
correlation method as a means of elucidating reaction pathways, applied to 5-coordinate tin and zinc
compounds; organometallic chemistry of arsenic, antimony and bismuth; oxidation levels,
structures, reactivities
Application of n.q.r. and e.s.r. spectroscopy to the structural and bonding problems of main group
compounds.
Title: Transition Metal Organometallic Compounds
Lecturer(s): Dr L J Farrugia
Aims: To consolidate and build on previous Level 1, 2 & 3 courses on the Transition metals, to
develop ideas on their organometallic compounds with respect to type, bonding and reactivity.
Objectives:
1. Know the types of organometallic ligands found (both s-donors and p-acid ligands) and be
able to rationalise their synergic bonding to transition metals, and their formal electron donating
counts. Be familiar with the experimental evidence for p back donation in carbonyl and olefin
compounds, and the basic reaction types associated with the more common ligands, i.e. oxidative
addition, hydride migration, reductive elimination.
2. Understand the metal-metal bonding in bimetallic carbonyls such as Mn2(CO)10 through the
isolobal principle. Know examples of larger carbonyl clusters with delocalised metal-metal bonds.
Know about the occurrence of multiple metal-metal bonds, and be able to rationalise the bonding in
terms of s, p and d bonds.
3. Know about the occurrence of metal hydrido compounds and multiple hydrido compounds
with dihydrogen ligands. Know the experimental evidence for non classical" hydrides, particularly
T1 NMR measurements.
4. Know a little about, and have a feel for the organometallic chemistry of all transition metals,
so they are not just symbols. In part this is achieved by the recommended readings.
Outline:
18-electron rule. Properties and synthesis of organotransition metal compounds and their
reaction types. Metal-metal bonds, carbonyl compounds, clusters, multiple metal-metal-bonds.
Metal-hydride compounds.
Title: Surface Chemistry and Heterogeneous Catalysis
Lecturer(s): Prof G Webb
Aims: To provide an introduction to the main concepts of heterogeneous catalysis through the study
of the chemistry and kinetics of reactions occurring at the catalyst surface. Particular emphasis is
given to the manufacture, characterization and testing of catalysts to demonstrate how catalysts can be
designed for specific reactions.
Objectives:
1. Know the definition of a catalyst as a substance which changes the rate of attainment of
equilibrium in a reacting system without causing any alteration to the free energy changes of the
reaction.
2. Appreciate that catalysis is purely a kinetic phenomenon.
3. Understand the concepts of physical and chemical adsorption at the surface of a solid and of
the differences between the two processes.
4. Be able to derive the Langmuir isotherm for (a) the adsorption of a single substance at a solid
surface and (b) the competitive adsorption of two gases at the same solid surface.
5. Appreciate the factors that are important for the design and preparation of supported
catalysts.
6. Have knowledge of experimental methods used to characterise heterogeneous catalysts.
7. Understand the derivation of appropriate kinetic expressions for unimolecular and
bimolecular surface-catalysed reactions and the use of kinetic measurements to determine reaction
mechanisms.
8. Understand the Langmuir-Hinshelwood and Rideal Eley mechanisms with refrence to
alkenes, alkynes and alkadienes.
9. Understand the terms structure sensitive/insensitive, selectivity and stereospecificity in
relation to catalytic processes.
10. Have knowledge of the catalysed hydrocarbon reforming reactions as discussed at various
points in the course.
Outline:
Introduction to the principles of heterogeneous catalysis by linking together concepts
developed in earlier physical. inorganic and organic chemistry lectures; physical and chemical
adsorption at the surface of a solid; interactions in supported metal/metal oxide catalysts; reference to
the design of catalysts tailored to specific industrial processes; the preparation of supported
metal/metal oxide catalysts exemplified both by model catalysts which are currently being developed
in the laboratory and well characterised industrial catalysts; the use of surface science techniques,
temperature programmed desorption and reduction, surface area determination and modern
spectroscopic methods in the characterisation of catalysts; rates and kinetic modes of reactions
exemplified by catalysed reactions used for large scale organic/inorganic synthesis and processes
designed to provide a cleaner environment; processes examined include hydrocarbon reforming,
hydrodesulphurisation and related processes and CO oxidation.
Title: Statistical Thermodynamics
Lecturer(s): Dr J H Dymond
Aims: To show how equilibrium thermodynamic property data for dilute gases and solids, and
chemical reaction rates, can be related to properties of the individual molecules
Objectives:
1. Derive the number of ways of distributing n indistinguishable particles among g degenerate
energy states.
2. Give the corrected Boltzmann statistics for the total number of arrangements of N particles,
where ni are in energy level ei which has a degeneracy gi
3. State the Boltzmann distribution law, and use it to determine the relative populations of
different energy levels.
4. Appreciate the meaning and importance of the molecular partition function, and relate it to
the total energy of a system.
5. Factorise the molecular partition function.
6. Give the expression for the translational partition function, and hence the contribution to the
energy and heat capacity at constant volume for an ideal gas
7. Give a statistical thermodynamic explanation for ideal gas expansion at constant
temperature.
8. Appreciate the impossibility of obtaining absolute energies.
9. Give the expression for the rotational partition function, and know the meaning of the
characteristic rotational temperature and the symmetry number.
10. Give the contribution to the energy and heat capacity at constant volume from rotational
motion.
11. Give the expression for the vibrational partition function, and know the meaning of the
characteristic vibrational temperature.
12. Calculate the contribution to the energy and heat capacity at constant volume arising from
vibrational motion.
13. Describe ortho and para-states of diatomic molecules, and understand the alternating
intensities to be found in rotational Raman spectra.
14. Calculate enthalpy changes for reactions.
15. Account for the temperature dependence of the heat capacities of solids.
16. Relate the Boltzmann expression for entropy to the classical entropy.
17. Give the statistical thermodynamic expression for entropy in terms of energy and the
molecular partition function.
18. Give the Sackur-Tetrode equation, and demonstrate that the dependence of entropy for an
ideal gas on T at constant V, and on V at constant T, agree with classical results.
19. Explain what is meant by residual entropy, and calculate values for this for certain systems.
20. Relate the Helmholtz and Gibbs energies to the molecular partition function.
21. Give approximate values for the translational, rotational, vibrational and electronic
contributions to the molecular partition function.
22. Explain chemical equilibrium in terms of the distribution of molecules among energy levels,
and hence understand the molecular factors that influence the position of equilibrium.
23. Describe transition state theory and derive and expression for absolute reaction rates
24. Calculate steric factors for reactions involving molecules of differing complexity
Outline:
This course is designed to show how equilibrium thermodynamic data for dilute gases and solids, and
chemical reaction rates, depend upon the properties of the constituent molecules.
Introduction - derivation of the numbers of ways of distributing indistinguishable particles among
degenerate energy levels corrected Boltzmann statistics and simple applications; the molecular
partition function (q); dependence of the internal energy on q factorisation of q; the contribution from
translational motion, and translational energy; absolute energies rotational partition functions and the
symmetry number; rotational energy and heat capacity contribution vibrational partition function, the
characteristic vibrational temperature and the contribution to the heat capacity electronic partition
function; effects of nuclear spin - ortho and para forms; relative intensities of rotational Raman
spectra enthalpy changes for chemical reactions; classical and statistical entropies.
Sackur-Tetrode equation for monatomics; residual entropy for simple diatomics and glasses; free
energy changes chemical equilibrium; simple collision theory of reaction rates activated complex
theory, and examples.
Title: Laser Spectroscopy
Lecturer(s): Dr J K Tyler
Aims: This course is intended to introduce the principles of laser operation in general and the
details of specific devices. Some important applications of lasers in chemistry and spectroscopy are
touched on.
Objectives:
1. The nature of radiative transitions and basic laser theory.
2. Ways of achieving population inversions.
3. Optical gain and feedback, and the criteria for pulsed and continuous operation.
4. Rare gas discharge lasers, molecular infrared gas lasers, hydrogen halide chemical lasers and
organic dye solution lasers.
5. Diode lasers.
6. Excimer lasers and super-radiance.
7. The laser as a spectroscopic source and as an excitation source for Raman spectroscopy.
8. Flash photolysis with lasers.
9. Multiphoton processes and infrared photochemistry.
Outline:
Radiative and non-radiative energy changes. Spontaneous and stimulated radiative processes
and basic laser theory. Practical realisation of laser action. Population inversion. The ammonia
maser. Optical gain and feedback. The ruby and neodymiun ion lasers. Criteria for pulsed and
continuous operation. Rare gas discharge lasers. Details of the He/Ne device. Molecular gas lasers
operating in the infrared region exemplified by the CO2/N2 system. Hydrogen halide chemical lasers.
Organic dye solution lasers.
Semiconductor levels and diode lasers. The N2 laser. Super-radiance. Excimer and
exciplex lasers. The nature of laser radiation. The laser as a spectroscopic source. Tunability. The
laser as an excitation source for Raman spectroscopy. Flash photolysis with lasers. Multiphoton
processes. Infrared photochemistry. Laser separation of isotopes.
Title: Modern Molecular Calculations
Lecturer(s): Dr B C Webster
Aims: To introduce the computer based methods which are available for the ab-initio calculation of
molecular properties and reaction paths.
Objectives:
1. Appreciate calculation strategies on large computers without becoming involved in details
of the programming and develop a critical attitude to the results obtained.
2. Describe the general structure of calculations of Hartree Fock molecular orbitals.
3. Understand the various type of basis sets and their influence on molecular results.
4. Describe how molecular geometry is optimised and reaction paths
determined.
5. Describe the general structure of calculations involving configuration interaction.
Outline:
After revision of some elementary ideas in quantum mechanics the techniques of modern
molecular computation and the range of contemporary computer programs are described.
Title: Chirality
Lecturer(s): Dr R D Peacock
Aims: The aims of the course are to provide an introduction to the occurrence and importance of
chirality; to explain how chiral molecules may be detected, resolved or synthesised and to give an
appreciation of circular dichroism spectroscopy and its use in determining the absolute configuration
of chiral molecules.
Objectives:
1. Understand the basic definitions of chirality - enantiomer, diasterioisomer, racemate. Have
an appreciation of the importance of chirality in the interaction of chiral molecules with natural
systems such as man.
2. Appreciate the idea of a chromophore. Know the common types of chromophore and the
transitions which they undergo.
3. Understand the concept of the polarisation of an electronic transition, of plane
polarised light and of plane polarised absorption spectroscopy. Understand how the polarisation of
a transition can be derived by multiplying the phase of the HOMO with that of the LUMO (or
higher unoccupied molecular orbital).
4. Be able to use phase multiplication to determine the polarisations of the p -> p* transition
of ethene and the d -> d* transition of the Mo2 chromophore and appreciate how the method can be
used to determine the polarisation (long or short axis) of the transitions of polyacenes such as
substituted benzenes, naphthalene and anthracene.
5. Understand how in the twisted Mo2 chromophore there is a transient helical charge
distribution during the d -> d* transition and how this charge distribution interacts differently with
left and right circularly polarised light leading to circular dichroism. Appreciate how the sense of
twist of the chromophore (and hence the absolute configuration) is related to the sign of the CD
spectrum.
6. Understand the concept of chirally coupled (organic) chromophores. Understand how the CD
spectrum of such a system is related to the chirality of the molecule. Be able to determine the chirality
of a pair of coupled chromophores from the sign of its CD spectrum.
7. Understand how enantiomers can interact in homochiral or heterochiral pairs of stacks.
Appreciate the molecular basis of diastereomeric interactions ("three point model").
8. Know the common methods of resolving chiral molecules.
9. Be able to describe, and appreciate the molecular basis of, the various methods of detecting
chiral molecules - chiral chromatography, chiral NMR reagents, chiral sensors.
10. Appreciate the molecular basis of asymmetric catalysis - particularly as applied to the
examples given in lectures.
Outline:
General definitions of chirality etc.; chromophores; polarisation of electronic transitions; the
alkene and dimolybdenum chromophores; twisted chromophores and circular dichroism; coupled
chromophores - bianthryls etc, use in determining absolute configuration; diasteriomeric interactions;
resolution of enantiomers; chiral GLC, chiral HPLC, chiral NMR shift reagents, chiral sensors;
asymmetric catalysis.
Title: Homogeneous Catalysis
Lecturer(s): Dr R J Cross
Aims: To obtain knowledge of the operations of a wide range of homogeneous catalysis systems in
actual applications, and to understand how information is derived about the working of such systems.
Objectives:
These will be issued during the course.
Outline:
Survey and revision of the reactions of transition metal and organometallic compounds which
operate in homogeneous catalysed reactions. Place of electron counting schemes in rationalising
catalysis reaction steps, illustrated by some simple catalysed reactions.
Ways of obtaining mechanistic information on catalytic processes, illustrated by
hydrogenation reactions at Williamson's catalyst.
Operation of specific processes, including Zelgles-Natta polymerisations, Wacker process,
SHOP process and olefin metallesis.
Chiral catalysis. Relationship of homogeneous processes to heterogeneous catalysis, and
ways of exploiting the advantages of both.
Title: Main Group Chemistry - Noble-Gas Chemistry
Lecturer(s): Prof T M Klapötke
Aims: To develop a knowledge of the main properties of noble-gas compounds and of their physical
nature.
Objectives:
1. Have a knowledge and understanding of the chemistry of binary noble-gas halides, and be
familiar with their structure and bonding.
2. Have a knowledge and understanding of the chemistry of binary xenon oxides and ternary
xenon oxofluorides, and be familiar with their structure and bonding.
3. Have a knowledge and understanding of the chemistry of xenon-carbon compounds, and be
familiar with their structure and bonding.
4. Have a knowledge and understanding of the chemistry of xenon-nitrogen and krypton-
nitrogen, and be familiar with their structure and bonding.
5. Know about theoretical aspects and ab initio computations concerning the existence of
ternary noble-gas compounds of the type NgBeO (Ng = noble-gas) and know about preparative aspects
of modern noble-gas chemistry and matrix isolation techniques.
6. Have a knowledge of the existence of noble-gas tungsten compounds and know about
preparative aspects of modern noble-gas chemistry and matrix isolation techniques.
Outline:
The course covers all areas of noble-gas chemistry: (i) structure and bonding, (ii) ab initio
computations (iii) orbital symmetry effects and kinetics, (iv) thermodynamics and (v) preparative
aspects.
It is assumed that the student has completed the relevant first, second and third year courses
on inorganic chemistry. Some elementary but very important topics, such as the VSEPR model
applied to noble-gas compounds are included for review and emphasis.
Data from advanced experimental techniques such as NMR (14N, 17O 19F, 129Xe) and
vibrational data obtained from matrix isolated species have been included where appropriate.
Structure and bonding; the VSEPR model, the electron domain model.
Thermodynamics; estimation of the heat of reaction by using a simple Born-Haber energy
cycle, estimation of the crystal lattice energy by using the Bartlett equation.
Title: Surface Chemistry and Catalysis
Lecturer(s): Drs D Lennon and D Stirling
Aims: To gain an understanding of what is meant by a catalyst surface and how the nature of the
active sites on the surface can be determined using a range of characterisation techniques. Also to
provide an understanding of how the mechanisms of surface catalysed reactions can be elucidated
using spectroscopic, kinetic and isotopic tracer techniques.
Objectives:
1. To have a knowledge of single crystal surfaces of metals and selected ultra-high vacuum
techniques than can be used for their characterisation, including X-ray and ultraviolet photoelectron
spectroscopies (XPS), (UPS), low energy electron diffraction (LEED), electron energy loss
spectroscopy (EELS) and Auger electron spectroscopy (AES).
2. To have an appreciation of the surfaces of typical catalysts and how the techniques
mentioned in (1) together with more conventional techniques such as infrared and uv/visible
spectroscopies used to gain information on the surfaces of these catalysts.
3. To have a knowledge of other characterisation techniques applicable to supported metal and
supported metal oxide catalysts including total surface area determination (BET), chemisorption
temperature programmed and diffraction techniques.
4. To have an appreciation of surface catalysed reactions and how spectroscopic, kinetic and
tracer techniques can be used to elucidate the mechanisms of these reactions.
5. To be able to interpret previously unseen mechanistic data using the skills developed in
objectives 1 to 4.
Outline:
This course will introduce the concepts of surface science an how techniques originally used
in the study of single crystals can be applied to supported catalysts typical to those used in an
industrial environment. The main emphasis will be on catalyst characterisation techniques and how
these can be used to gain mechanistic information in typical surface catalysed reactions.
Title: Chemistry and Pharmacology of Anti-cancer Drugs
Lecturer(s): Prof D J Robins, Dr A D Lewis (Quintiles)
Aims: To discuss the main agents used in the treatment of cancer in terms of synthesis, chemistry,
metabolism and mode of action.
Objectives:
1. Know about abnormal cell growth and its causes and possible treatments.
2. Recognise different types of alkylating agents, their synthesis, mechanism of action and
pharmacology.
3. Understand the concept of antimetabolites with synthesis and mode of action of examples
such as 5-fluorouracil and methotrexate.
4. Understand hypoxia in tumours and selectivity of action achieved by bioreductive agents
containing quinones or N-oxides; know about the mode of activation and action of bioreductive agents
such as mitiomycin C.
5. Know about natural products used as anticancer agents, particularly doxorubicin with partial
synthesis and mode of action; topoisomerase inhibitors and microtubule inhibitors.
6. Understand the importance of growth factors and inhibition of signalling processes by drugs
as new targets.
7. Know about the synthesis, spectroscopy and instability of tyrosine kinase inhibitors and
erbstatin.
Outlines:
Cancer Biology: a disease of abnormal growth and cellular proliferation; causes and methods of
treatment; development of anti-cancer drugs; importance of selectivity; classes of anti-cancer agents
including alkylating agents, antimetabolites, bioreducible compounds, natural products and
compounds which interfere with cell signalling processes; pharmacokinetics and mechanism of
action; drug design and drug resistance; drug development based on mechanism of action.
Chemistry of anticancer drugs: alkylating agents including nitrogen mustards, cyclophosphamide,
nitrosourea (synthesis action and interaction with DNA); antimetabolites including 5-fluorouracil and
methotrexate (synthesis and mechanism of action); natural products such as doxorubicin and taxol
(partial synthesis, spectroscopic characterisation); tyrosine kinase inhibitors including active
compounds made in this Department ( synthesis and spectroscopic characterisation).
Title: Modern Synthetic Methods
Lecturer(s): Dr E W Colvin
Aims: To introduce unfamiliar reactions and concepts of high current activity and interest, and to
give a fairly detailed overview of the methodology of modern synthetic organic chemistry.
Objectives:
1. Appreciate the concept of polarity reversal, or umpolung.
2. Understand and be able to discuss, Sharples enantioselective epoxidation and kinetic
resolution of allylic alcohols.
3. Understand, and be able to discuss, enantioselective epoxidation and dihydroxylation of
simple alkenes.
4. Understand the use of tin hydrides in reductive deoxygenation, and deselenylation, and
appreciate the synthetic value of the intramolecular trapping of the intermediate radicals.
5. Understand the basis of the control that the b -effect and a -anionoid stabilisation can play in
organosilicon chemistry.
6. Understand the chemistry of vinylsilanes, in terms of their preparation and reactivity.
7. Understand the chemistry of allylsilanes, in terms of their preparation and reactivity
8. Understand the chemistry of arylsilanes, in terms of their preparation and reactivity.
9. Know the principles and synthetic utility of Peterson Olefination.
10. Understand the chemistry of a,b-epoxysilanes, in terms of their preparation and reactivity.
11. Know the principles and synthetic utility of the oxidative cleavage of C-Si bonds.
12. Understand the chemistry of silyl ethers, in terms of their preparation and utility.
13. Understand the chemistry of silyl enol ethers, in terms of their preparation and wide synthetic
utility.
14. Understand the basic principles of organosulphur chemistry.
15. Understand the chemistry of thioacetals, in terms of their preparation and synthetic utility.
16. Understand the varied chemistry of sulphoxides.
17. Understand the chemistry of anions to sulphur in its various oxidation states.
18. Understand the chemistry of sulphonium and sulphoxonium ylides as methylene transfer
reagents.
Outline:
Ti/Mn/Os: Sharpless enantioselective epoxidation of allylic alcohols; kinetic resolution of
allylic alcohols; Jacobsen enantioselective epoxidation of simple alkenes; Sharpless enantioselective
dihydroxylation.
Sn: use of tin hydrides in reductive dehalogenation, including cyclisation of radical
intermediates with examples; Barton deoxygenation; selenolactonisation and reductive removal.
Si: basic principles; b-effect and a-anion (oid) stabilisation; growth of organosilicon
chemistry.
Vinylsilanes: preparation; reactivity towards electrophiles; ipso desilylation and
stereochemistry.
Allylsilanes: preparation; reactivity towards electrophiles - regiochemistry and stereochemistry;
formal anion generation.
Arylsilanes: preparation; ipso desilylation.
b-Hydroxysilanes: preparation; Peterson Olefination.
a, b-Epoxysilanes: preparation; acid-catalysed opening.
Oxidative cleavage of C-Si bonds: mechanism; synthetic utility.
ROSiMe3 and ROSiMe2 tBu: preparation, use, cleavage.
Silyl enol ethers and ketene acetals: preparation; spectrum of reactivity including [4+2], Ireland-
Claisen.
S and Se: nomenclature in various oxidation states; basic principles; formation and cleavage of C-S
bonds; thioacetal preparation and cleavage - hydrolytic and reductive.
Reactions of sulphoxides: DMSO as and oxidant; Swern and mechanism; Corey DMS/NCS/Et3N;
Pummerer rearrangement.
[2,3]-Sigmatropic rearrangements: allylic sulphoxides; retro-ene (also with selenoxides); penicillin ®
cephalosporin.
a-Anions: thioethers, 1,3-dithianes; DMSO, chiral sulphoxide anions; sulphones, Julia Coupling,
chrysanthemic acid synthesis.
Sulphonium and sulphoxonium ylides: dimethylsulphonium methylide (hard) and
dimethylsulphoxonium methylide (soft); contrasting chemoselectivity with enones.
Title: Asymmetric synthesis
Lecturer(s): Dr R C Hartley
Aims: To introduce the different types of asymmetric synthesis. To concentrate on methods of
asymmetric induction which involve the formation of C-C bonds. To illustrate these methods with
syntheses of biologically active molecules and to show the importance of organometallics in carrying
out unconventional transformations.
Objectives:
1. Describe the different types of asymmetric synthesis; assess the advantages and
disadvantages of each approach with particular reference to atom economy and enantiomeric purity;
explain the importance of enantiopure drugs.
2. Explain how enolate geometry is controlled and how chelation control gives rise to
diastereoselectivity in aldol reactions (E enolate gives anti; Z enolate gives syn).
3. Describe the chiral auxiliary approach to asymmetric synthesis using Evans' oxazolidine
chemistry, apply Evans' oxazolidine chemistry to the synthesis of enantiopure compounds, and
explain how absolute and relative stereochemistry is controlled in reactions using this chemistry.
4. Count electrons in a metal complex, recognise and explain the importance of coordinative
saturation, and describe the basic types of reaction found in most catalytic cycles (association and
dissociation; oxidative addition and reductive elimination; ligand to metal migration and metal to
ligand migration; nucleophilic attack on ligands).
5. Describe the mechanism of Pd0 catalysed cross-coupling reactions (in general and for
particular examples), explain any restrictions to the substrates, and apply these reactions to synthesis.
6. Describe and give examples of the different types of ligand chirality (centre, planar, axial),
and assign R and S configuration to the different chiral entities.
7. Explain dynamic kinetic resolution and its application in asymmetric cross-coupling
reactions.
8. Describe the mechanism of Pd0 catalysed allylic alkylations (in general and for particular
examples) and apply these reactions to synthesis.
9. Explain the ligand design in asymmetric Type I and Type IIa allylic alkylation reactions, in
particular the use of C2 symmetric and P,N ligands, and give examples of known C2 ligands and P,N
ligands.
Outline:
Overview of asymmetric synthesis (including concept of atom economy); Evans' oxazolidone
chemistry: (i) asymmetric enolate alkylation (ii) asymmetric aldol condensation (chelation control,
face selectivity) (iii) applications in synthesis. Basic organotransition metal chemistry (electron
count in complexes). Pd0 catalysed cross-coupling reactions and their application to synthesis.
Different types of ligand chirality. Catalytic asymmetric cross-coupling and dynamic kinetic
resolution. Pd0 catalysed allylic alkylation. Asymmetric type I, and type IIa (C2 symmetric and P,N
ligands) allylic alkylations.
Title: Enzymes in Organic Chemistry
Lecturer(s): Dr R A Hill
Aims: To understand the methods involved in determining enzyme mechanisms and the knowledge
of these mechanisms can be applied to using enzymes as reagents and the design of model enzymes.
Objectives:
1. Understand generally the structures of enzymes.
2. Understand how determination of the stereochemical features of enzyme reactions can be
used to determine the mechanisms of these reactions.
3. Describe how the stereochemistry features of alcohol dehydrogenase reactions were
established.
4. Describe how the stereochemistry of various enzymic addition/elimination reactions was
determined and how this gives an insight into the way enzymes work.
5. Understand how enzymes are such efficient catalysts and how they may be used in organic
synthesis.
6. Describe some of the ways enzymes are used in industry.
7. Discuss the use of reductases in synthetic organic chemistry to produce homochiral
compounds from achiral compounds and racemic mixtures.
8. Describe the mechanisms and stereochemical features of hydroxylating enzymes.
9. Discuss the use of hydrolytic enzymes in organic reactions.
10. Describe how the concepts of enzymic catalysis have been tested and utilised using enzyme
models and biomimetric reactions.
11. Apply the principles of this course in solving problems of related enzyme reactions.
Outline:
The mechanism and stereochemistry of alcohol dehydrogenase and how a knowledge of the
stereochemical outcome of of alcohol dehydrogenases help the understanding of other enzyme
reactions; a series of elimination/addition enzyme reactions will be studied to look at the various
methods of examining enzyme mechanisms and to make generalisations about the requirements for
efficient enzyme reactions. The enzymes involved are: phenylalanine ammonia lyase, fumarase,
aconitase, dehydroquinate dehydrase and aldose-ketose isomerase.The use of enzymes as organic
reagents, their advantages and disadvantages; some industrial applications of enzymes; the use of
alcohol dehydrogenases including the stereospecific and regiospecific aspects, use in resolution of
enantiomers and generation of chiral compounds from achiral substrates; hydroxylating enzymes and
the mechanism of hydroxylation of unactivated carbons and aromatic compounds including
phenylalanine hydroxylase and tyrosine hydroxylase (mention of NIH shift). Mono and dioxygenases
and phenol oxidative coupling as examples of enzymes for performing "chemically difficult"
reactions.
Biomimetic chemistry, including intramolecular catalysis, Breslow's benzophenones,
cyclodextrins, cyclophanes, crown ethers and related compounds.
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