CHEM 320 : Design and Reactivity of Inorganic Compounds
2020 Semester One (1203) (15 POINTS)
Capabilities Developed in this Course
|Capability 1:||Disciplinary Knowledge and Practice|
|Capability 2:||Critical Thinking|
|Capability 3:||Solution Seeking|
|Capability 4:||Communication and Engagement|
|Capability 5:||Independence and Integrity|
- Understsnd and interpret multinuclear NMR spectra and use this as a tool for determination of inorganic molecular structure. (Capability 1, 2 and 3)
- Understand the principles of crystal field theory and apply this to interpret and explain the electronic spectra and magnetic properties of transition metal complexes. (Capability 1, 2 and 3)
- Understand the thermodynamic and kinetic aspects of inorganic reactions and to be able to use that knowledge to explain reaction mechanisms relating to ligand substitution and electron transfer reactions. (Capability 1, 2 and 3)
- Describe the different methods of forming bonds between main group elements and carbon, as well as the properties and uses of these compounds. (Capability 1)
- Identify and explain the products from main-group transformations to make non-carbon rings and polymers. (Capability 1 and 2)
- Describe and understand the bonding models used to explain the interactions between transition metals and unsaturated organic molecules, and to use that knowledge to predict the structural and spectroscopic properties of these compounds. (Capability 1, 2 and 3)
- recognise and understand oxidative addition, reductive elimination, migratory insertion/de-insertion, beta-hydrogen elimination and ligand substitution as key organometallic reaction types, and to be able to use these to explain the reactions described in the lectures. (Capability 1 and 2)
- Apply organometallic chemistry concepts and principles to understand and explain the industrially important transition metal catalysed reactions described in lectures. (Capability 2 and 3)
- Describe and understand the central role coordination compounds play in biological systems, and the application of metal compounds in the treatment of diseases, for imaging and diagnosis. (Capability 1 and 2)
- Obtain the skills necessary to carry out practical laboratory work that reinforces the concepts, principles and knowledge gained in the course, and to communicate the outcomes effectively. (Capability 1, 2, 3, 4 and 5)
|Final Exam||50%||Individual Examination|
|Assessment Type||Learning Outcome Addressed|
1. Multinuclear NMR in Inorganic Chemistry
Occurrence of I = ½ isotopes 1H, 13C, 31P, 19F, 29Si, 195Pt, 103Rh, 119Sn, 117Sn.
Interpretation of multinuclear NMR and use as a tool for assignment of inorganic molecular structure.
Use selected examples of compounds from all categories above to illustrate principles.
2. Electronic spectra of coordination complexes (including a review of crystal field theory and ligand field theory)
Outline how electron-electron repulsions perturb energy levels in ions and complexes
Identify the free ion terms, the ground state term and the excited state terms in Tanabe-Sugano diagrams
Use Tanabe-Sugano diagrams to interpret d-d electronic spectra by assigning transitions to absorption bands
Use Tanabe-Sugano diagrams to calculate Δ
Calculate the Racah parameter B for a complex and explain its significance
Compare the Racah parameter B for a complex with that for the free ion
Explain the origin and selection rules for electronic transitions in complexes
Relate the selection rules to the relative values of the extinction coefficient ε
Describe the origin of charge transfer spectra in complexes, including LMCT and MLCT bands
Identify which characteristics of metal complexes are likely to give rise to LMCT or MLCT bands
Differentiate between d-d and charge transfer bands in an electronic spectrum
Explain the phenomena of luminescence and phosphorescence
3. Photochemical reactions
Photoinduced electron transfer and solar cell using ruthenium complexes
Using [Ru(bipy)3]3+ as case study, explain how redox properties in the ground state and an excited state differ
Describe how the properties of this complex can be exploited in a dye-sensitised solar cell
4. Magnetic properties of transition metal complexes
Define diamagnetism and paramagnetism and describe the electronic properties that give rise to the diamagnetic and paramagnetic effects
Define magnetic susceptibility, including the three quantities: volume susceptibility (χ), gram susceptibility (χg) and molar susceptibility (χm)
Describe methods of measuring magnetic susceptibility
Describe the relationship between magnetic susceptibility (χm) and magnetic moment (μeff) using the expression μeff = 2.828(χmT)1/2
Relate μeff measured by experiment to the spin only value μ = 2[S(S + 1)]1/2 or μ = [n(n + 2)]1/2 and determine the number of unpaired electrons for a complex
Show that the number of unpaired electrons for a complex is consistent with the metal, oxidation state, coordination geometry and ligands present in the complex
Using iron dialkyldithiocarbamate complexes as a case study, describe the phenomenon of intermediate spin for a square pyramidal iron(III) complex
Using iron dialkyldithiocarbamate complexes as a case study, describe the phenomenon of spin equilibrium in iron(III) complexes
B. Transition Metal Organometallic Chemistry
Classification of organometallic compounds, bond polarity, bond type (covalent, multicentre, multiple bonds, π-complexes),
The 18-electron rule (including description, number of electrons formally donated by ligands, exceptions and examples).
2. Transition metal carbonyls.
Preparation and physical properties: Structures, simple carbonyls of the first transition series, polynuclear carbonyls, bonding, experimental evidence for bonding models, isoelectronic and isostructural species, IR frequencies and symmetry.
Reactions of binary metal carbonyls: Substitution, electron transfer catalysis, nucleophilic attack, formation of anions, reactions of carbonylate anions.
Other ligands related to CO: TM complexes of isocyanide, cyanide, thiocarbonyl, carbene (including preparation, structure and bonding), carbyne, nitrosyl and PR3 ligands.
3. σ-Donor/π-Acceptor Ligands.
Simple alkene complexes: Syntheses, bonding, structural studies, hindered rotation and NMR studies, complexed polyalkenes, reactions of coordinated alkenes, heteroalkene and heteroallene complexes.
Alkyne complexes: Mononuclear complexes, dinuclear compexes, special alkyne complexes (including benzyne), alkyne complexes in organic synthesis (including metal stabilised propargyl cations, oligomerisation of alkynes, substituted benzene synthesis, pyridine synthesis, synthesis of homocyclic systems, the Pauson-Khand reaction), heteroalkyne complexes.
Allyl and –enyl Complexes: π-Allyl complexes (including structure and bonding and uses in organic synthesis, cyclic polyene and polyenyl complexes, half-sandwich complexes, multi-decker sandwiches, ferrocene (including history of discovery, structure, bonding, reactions and special features of ferrocene), cobaltocene, nickelocene, coordination modes of the cyclopentadienyl anion (including NMR studies), other carbocyclic rings (including 4- and 6-membered rings).
4. Transition Metal-Carbon σ-Bonds.
Preparation of TM σ-alkyls and aryls: Metal anion with RX, metal halide with carbanion, from transition metal hydrides, oxidative addition, other methods.
Kinetic and thermodynamic stabilities of TM alkyls: General considerations, low energy decomposition routes available to TM alkyls (including β-hydrogen elimination, α-hydrogen abstraction, reductive elimination, ligand hydrogen abstraction), perfluoroalkyl complexes.
5. Important Reaction Classes in TM Organometallic Chemistry.
Coordinatively saturated and unsaturated complexes, insertion reactions (including details of mechanisms), oxidative addition and reductive elimination.
6. Organometallic Catalysis.
Introduction: Mode of action of TM complexes in catalysis, heterogeneous and homogeneous catalysts.
The Wacker Process: Overall reaction, industrial importance and typical industrial parameters, catalytic cycle discussed in terms of fundamental organometallic steps.
Hydrogenation of Alkenes: Scope, conditions, catalytic cycle involving Wilkinson’s catalyst, asymmetric hydrogenation, L-Dopa synthesis.
Monsanto acetic acid process: Industrial importance, catalytic cycle, fundamental steps in the catalytic cycle.
Hydroformylation: Industrial significance, variety of products formed, different catalysts, catylitic cycles involving HCo(CO)4 and RhH(CO)(PPh3)3, individual steps involved in these processes and comparisons between them.
Oligomerisation and polymersation: Cyclisations of acetylene and butadiene, polymerisation on alkenes, different tacticities of polymers from propene, mechanisms.
C. Bio-inorganic chemistry
Bioinorganic Chemistry is an interdisciplinary research area and deals with all aspects of metals and their biological functions. The lectures will provide insight into the central role of coordination compounds in nature, and point out the potential for application as drugs. Selected examples will lead the students to the understanding of fascinating processes occurring in bioinorganic chemistry.
• General aspects of bioinorganic chemistry
• Biological ligand systems
• Role of metals in nature
• Metals and proteins (Fe, Zn, Mn, etc.)
• Metals and toxicity
• Metal compounds in treatment of different diseases imaging and diagnosis
D. Kinetics and Thermodynamics in Inorganic Chemistry and Main-Group Chemistry
1. Kinetics and Thermodynamics in Inorganic Chemistry
Investigating the kinetics of a reaction and understanding the thermodynamics of the transformation help to build an accurate picture of the corresponding energetic landscape and provide insight into the reaction mechanism(s) involved. Lectures will cover:
Terms and equations: equilibrium constant, ground state, transition state, intermediate, rate constant, activation energy, reaction order, rate law, Arrhenius Equation, Eyring Equation, entropy, enthalpy, Gibbs free energy, inert/labile, nucleophilicity/electrophilicity, basicity/acidity
Ligand substitution reactions: trans effect/trans influence, associative/dissociative/Interchange mechanisms
2. Main-Group Chemistry
The chemistry of the s- and p- blocks in the periodic table is an ever expanding field with many recent advances in the area. The lectures will cover:
Fundamentals in synthesizing E-C, E-E and E-E’ bonds (E, E’ = main-group element): examples from Groups 1, 2, 12, 13-15.
You must pass both the theory (combined tests and final exam) and the practical work (the 6 assigned laboratory reports with associated samples) to gain an overall pass for the course.
The health and safety requirements detailed for the laboratory sessions must be adhered to.
This course is a standard 15 point course and students are expected to spend 10 hours per week involved in each 15 point course that they are enrolled in.
For this course, you can expect 36 hours of lectures, 12 one hour tutorials, 18 hours of laboratory work (6 x 3 hours), 42 hours of reading and thinking about the content and 42 hours of work on assignments and/or test preparation.
Course materials are made available in a learning and collaboration tool called Canvas which also includes reading lists and lecture recordings (where available).
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During the course Class Representatives in each class can take feedback to the staff responsible for the course and staff-student consultative committees.
At the end of the course students will be invited to give feedback on the course and teaching through a tool called SET or Qualtrics. The lecturers and course co-ordinators will consider all feedback.
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Student Charter and Responsibilities
The Student Charter assumes and acknowledges that students are active participants in the learning process and that they have responsibilities to the institution and the international community of scholars. The University expects that students will act at all times in a way that demonstrates respect for the rights of other students and staff so that the learning environment is both safe and productive. For further information visit Student Charter (https://www.auckland.ac.nz/en/students/forms-policies-and-guidelines/student-policies-and-guidelines/student-charter.html).
Elements of this outline may be subject to change. The latest information about the course will be available for enrolled students in Canvas.
In this course you may be asked to submit your coursework assessments digitally. The University reserves the right to conduct scheduled tests and examinations for this course online or through the use of computers or other electronic devices. Where tests or examinations are conducted online remote invigilation arrangements may be used. The final decision on the completion mode for a test or examination, and remote invigilation arrangements where applicable, will be advised to students at least 10 days prior to the scheduled date of the assessment, or in the case of an examination when the examination timetable is published.