Modules - University of Liverpool

Module Details

The information contained in this module specification was correct at the time of publication but may be subject to change, either during the session because of unforeseen circumstances, or following review of the module at the end of the session. Queries about the module should be directed to the member of staff with responsibility for the module.

Title	METALS AND METALLOIDS OF THE p AND d-BLOCKS
Code	CHEM214
Coordinator	Dr JA Iggo Chemistry J.A.Iggo@liverpool.ac.uk
Year	CATS Level	Semester	CATS Value
Session 2016-17	Level 5 FHEQ	Second Semester	15

Pre-requisites before taking this module (or general academic requirements):

CHEM111 Completion of first year of MChem of BSc programme (or suitable accepted alternative)

Aims

Aims:

This module is an introduction to the co-ordination and organometallic chemistry of 3d transition metals, and will encompass theory, physical methods and descriptive chemistry.

The aims of the module are:

To outline how bonding theories (valence bond, crystal field, ligand field) have been developed by chemists to rationalise important properties of the d–block elements, many of which distinguish them from organic and main group compounds
To illustrate the chemistry of the transition elements by a detailed study of three groups, Ti/Zr/Hf, Fe/Ru/Os and Ni/Pd /Pt, including:

Discovery, isolation and technological importance of the elements and their compounds
A survey of the chemistry of the different oxidation states and a comparison of the 3d elements with their heavier 4d and 5d relatives
Brief comparisons/contrasts with neighbouring groups of elements.

To introduce the theory underlying the use of appropriate physical and spectroscopic techniques for characterising d–block complexes, and examples of their application.
To introduce the chemistry, and some applications, of complexes in low oxidation states, including:

CO as an examplar of a p-acceptor ligand
3d Metal carbonyl complexes
Analogous ligands, e.g. NO, RNC
The 18-electron rule; what it is, and why it applies to these complexes.

To introduce the chemistry, and some applications, of p-block elements and compounds.

Learning Outcomes

By the end of the module students should:

Show an understanding of the concepts, applications and limitations of the different bonding theories relevant to transition-metal complex chemistry, and be aware of their relative relevance in different chemical contexts.
Be able to identify key elements of the structures of transition-metal complexes, and apply their knowledge of spectroscopic and physical techniques to work out the correct structure for a complex, given relevant chemical and spectroscopic information.
Be able to describe the social, economic and technological importance of selected transition elements.
Understand and be able to describe the significance of the syntheses, characterisation and chemistry of 3d metal complexes encountered in the pract ical module, CHEM245.
Understand the origin of the18-electron rule, its application and the sort of complexes to which it applies.

Teaching and Learning Strategies

Lecture -

Tutorial -

Assessment -

Syllabus

Essential concepts in Transition Metal Chemistry – An Introduction

Introduction to transition metal complexes. Coordination complexes and coordinate bonds. Oxidation state. Coordination number. Atomic d orbitals, dⁿ configuration.
Ligands, hard and soft donors. Electroneutrality.
Geometry, and isomerism.
Formation of complexes in solution. Stability constants. The chelate effect.
Crystal field theory. The basis of crystal field theory (CFT) for octahedral complexes. The origin of D. Factors affecting size of D. Colours in transition metal complexes; d–d transitions, selection rules. Charge transfer transitions.
Magnetic properties. High–spin and low–spin complexes. Magnetic moment, spin–only formula.
Crystal field stabilisation energy (CFSE). Favoured geometries, ionic radii, hydration enthalpies, latticed energies. Kinetic vs thermodynamic stability of complexes. Irving-Williams series.

Further Bonding in Transition Metal Complexes

Magnetic properties. Spin–only formula. Distinguishing high– and low–spin cases. Colours in transition metal complexes – how they arise. d–d Transitions. Selection rules. The d¹ case.
Charge transfer bands. Chemical evidence for CFSE. Its effect on chemistry of some metal ions.
The Jahn–Teller effect. How it arises. Its effect on (i) structure, (ii) chemistry, (iii) spectra of complexes. Geometries other than octahedral: 4–coordination.(i) Tetrahedral and (ii) square planar complex es in CFT terms. Factors favouring (i) square planar and (ii) tetrahedral complexes.
Where CFT breaks down. Covalence in metal–ligand bonds. Spectrochemical series revisited. Molecular orbital theory – revision. Its application to complexes. Comparison of MOT and CFT pictures for octahedral complexes. p –Bonding in complexes. High and low oxidation state complexes and their stabilisation by p–donor and p–acceptor ligands.

Transition Metal Descriptive Chemistry

Transition metal descriptive chemistry: introduction. Trends across the d–block: oxidation state stabilities, with examples. Differences between 3d and 4d/5d elements.
The early transition elements: Titanium, zirconium and hafnium chemistry.
Mid–transition metals: The chemistry of ruthenium and osmium, and comparisons with iron.
Late transition elements: The chemistry of nickel.
Late transition elements: The chemistry of palladium and platinum, and comparisons with nickel.

Transition Metal Complexes Containing CO and other p-Acceptor Ligands

Introduction to non-classical complexes containing p-acid ligands. 18 electron rule, bonding picture and comparison with classical complexes; synergistic bonding.
Preparation, structure and bonding, chemical properties, reactivity and uses of:

Binary metal carbonyls - preparation, characterisation, physical and c hemical properties.
Bonding modes and electronic structure.
Metal carbonyl hydrides
Complexes containing PR₃ and other p -acceptor ligands - electronic and steric effects and other p -acceptor ligands - electronic and steric effects.

Recommended Texts
Reading lists are managed at readinglists.liverpool.ac.uk. Click here to access the reading lists for this module. Explanation of Reading List:

Teaching Schedule

	Lectures	Seminars	Tutorials	Lab Practicals	Fieldwork Placement	Other	TOTAL
Study Hours	32		5			3	40
Timetable (if known)
Private Study							110
TOTAL HOURS							150

Assessment
EXAM	Duration	Timing (Semester)	% of final mark	Resit/resubmission opportunity	Penalty for late submission	Notes
Unseen Written Exam	3 hours	second	80	Yes	Standard UoL penalty applies	Assessment 2 Notes (applying to all assessments) Assessed problem sets This work is not marked anonymously Written Examination The examination will: (1) allow students to demonstrate an understanding of transition-metal chemistry, (2) test students' problem-solving skills in various aspects of transition-metal complex chemistry. (3) test students' ability to construct cogent arguments.
CONTINUOUS	Duration	Timing (Semester)	% of final mark	Resit/resubmission opportunity	Penalty for late submission	Notes
Coursework	5 x 1-hr sessions	second	20	No reassessment opportunity	Standard UoL penalty applies	Assessment 1 There is no reassessment opportunity,