CHEM 320 : Design and Reactivity of Inorganic Compounds

A selection of the most recent developments in contemporary inorganic chemistry will be covered. Topics include selected physical properties of coordination compounds such as multinuclear NMR spectroscopy, UV-vis spectroscopy, magnetism, redox chemistry and photochemistry, the organometallic chemistry and catalytic reactions of transition elements, bioinorganic and medicinal inorganic chemistry, the kinetics and thermodynamics of ligand substitution reactions, main-group organometallic chemistry and main-group polymers. The laboratories provide an important complementary experience in the synthesis and measurement of physical properties for selected inorganic compounds.

This course builds on the inorganic and physical chemistry concepts introduced in CHEM 220, or CHEM251 and 253. Areas of special focus include selected important physical techniques that are key to the understanding and characterisation of inorganic compounds, kinetics and thermodynamics as applied in inorganic chemistry, the organometallic chemistry of the transition elements, bio-inorganic chemistry, and main group chemistry. The course is designed to enable students to gain a wide appreciation of different aspects of modern inorganic chemistry and to develop critical thinking and problem solving skills in this key area. This course is important because it equips students with crucial core knowledge and skills that are essential for a comprehensive understanding of the modern discipline of chemistry. The course also provides students with  key foundational knowledge and skills to progress smoothly to higher, research-based degrees in chemistry (including BSc(Hons), MSc and PhD), or alternatively, to take advantage of employment opportunities in any areas where a broad knowledge of chemistry and/or proficiency in critical thinking is required.

Prerequisite: 15 points from CHEM 220, 251, 253

By the end of this course, students will be able to:

A. Physical methods in inorganic chemistry.
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  
1. Introduction.   
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.

Campus Experience or Online

This course is offered in two delivery modes:

Campus Experience

Attendance is required at scheduled activities including labs/tutorials to complete/receive credit for components of the course.
Lectures will be available as recordings. Other learning activities including tutorials will be available as recordings.
The course will include live online events including tutorials.
Attendance on campus is required for the tests/exam.
The activities for the course are scheduled as a standard weekly timetable delivery.

Online

Attendance is expected at scheduled online activities including tutorials to complete/receive credit for components of the course.
The course will include live online events including tutorials/lectures and these will be recorded.
Where possible, study material will be released progressively throughout the course.
This course runs to the University semester timetable and all the associated completion dates and deadlines will apply.

The delivery mode of this course may change in accordance with changes to New Zealand Government recommendations. Updates for this course will be provided on the course Canvas page.