Cláudio N. Verani
Associate Professor
Department of Chemistry, Rm. 143
5101 Cass Ave.
Detroit, MI 48202
Phone: (313) 577-1076
Email: [email protected]
CHM 8090 - Advanced Topics in Inorganic Chemistry
Principles, Methods, and Trends in Modern Coordination Chemistry
Fall term 2008
Frequency: Mondays, Wednesdays, and Fridays 1:55 –2:50 pm,
Room: State Hall 112
Course length:
Start January 11, 2010
End: May 4, 2010
Office hours: anytime by previous appointment
Enrolled students (as by January 8, 2010):
1. Derek Averill
2. Debashis Basu
3. Asha Priyadararshani Hitihami Mudiyanselage
4. Lin, Yunfei
5. Zavada, Mark Andrew
Tentative Syllabus:
I.
Description.
This course is based on a number of topics considered fundamental for the inorganic chemist.
These topics are also relevant for chemists working with analytical, biochemical, organic, and physical
projects. The focus is on theoretical and experimental facts on transition metal behavior, ligand
design, and instrumental methods. Based on several sources ranging from textbooks to classic and
recent scientific articles, this course aims at a class size between 5 and 15 students interested in
seminar- and writing-intensive activities. Topics to be discussed include the following:
● Metals: the inorganic building blocks for Coordination Chemistry
● Ligands: the organic building blocks for Coordination Chemistry
● Techniques and methods used in Coordination Chemistry
● Modern trends in Coordination Chemistry
II. Detailed Contents.
1. Introduction:
● Research modus-operandi, and why is this course useful
CHM 8090: Advanced Topics in Inorganic Chemistry 2. ● Cosmologic origin of the chemical elements (added, 2010W)
● Historical review, Werner, Jørgensen and the early days of coordination chemistry
3. Essential Techniques: (added, 2008F)
● The Essentials: Melting points and elemental analyses (added, 2008F)
● Spectroscopic methods : IR spectroscopy for ligands, metals and counterions
● Spectrometric methods : ESI mass analysis (added, 2008F)
● Spectroscopic methods II: UV-visible spectroscopy for CT & d-d transition (added, 2008F)
● Diffractometric methods: X-ray Crystallography (added, 2008F)
3. Metals: the inorganic building blocks for Coordination Chemistry i
● Structures and isomers
● Ligand Field Theory
● 3d- transition metals
● 4d and 5d transition metals
● Inorganic reaction mechanisms (Expanded, 2008F)
4. Ligands: the organic building blocks for Coordination Chemistry
● Ligand planning, synthesis, and laboratory skills;
●Open-ring ligands:
 Simple amines
 Bipyrydin, phenantroline & co.
 Aromatic amines I (pyrroles, pirazoles, imidazoles, oxadiazoles, thiadiazoles)
 Aromatic amines II (pyridazines, pyrimidines, pyrazines)
 Tripodal ligands: TREN, TMPA, Pyrazolylborates, asymmetric systems
 Pendant arm ligands
 Schiff base ligands & amine-aldehyde condensation
●Open-chain polydentate ligands
 Multistep asymmetric design
● Ligands for modular synthesis:
 Oxalato, thioxalato & anilato bridges
 Oxamato modules
 Oxamido modules
 Oximato modules
●Redox-responsive ligands
 Thiolenes (added, 2008F)
 Substituted phenols
 Catechols & aminocatechols
 Aminophenols
●Macrocyclic ligands:
 Template effect
 Simple cyclic amines: tacn, cyclan & co.
 Other cyclic amines incorporating S and O
 Porphyrins & Phthalocyanins
C. N. Verani Winter 2010 2
CHM 8090: Advanced Topics in Inorganic Chemistry  Robson type ligands and its variations
 TAAB & TRI
 Crown ethers
 Sepulchrates & other cage ligands (3D macrocycles)
5. Techniques and methods used in Coordination Chemistry:
● Electrochemistry & spectroelectrochemistry: study of redox processes (added, 2008F)
● Surface methods I: Self assembly of mono layers (added, 2008F)
● Surface methods II: Langmuir-Blodgett films and compression isotherms (added, 2008F)
6. Modern trends in Coordination Chemistry:
● Bioinorganic chemistry
● Catalysis
 Metal-catalyzed polymerization
 Atmospheric-relevant transition metal-catalyzed Processes
● Chemical Vapor and Atomic Layer Deposition (added, 2008F)
● Dyes and inks
● Computational methods in coordination chemistry
● Metal-containing Soft Materials
 Metallosurfactants
 Metallomesogens and other soft materials
 Metallopolymers
● Metal-based Molecular electronics:
 Molecular magnets
 Molecular switches
 Self assembly on responsive films
● Metals in medicine
 Vanadium Compounds as Insulin Mimics
 Platinum-Based Antitumor Drugs
 Non-Platinum Antitumor Drugs (added, 2008F)
 Gold-Based Therapeutic Agents
 Technetium Small Molecule Radiopharmaceuticals
 Therapeutic Radiopharmaceuticals
 Gadolinium(III) Chelates as MRI Contrast Agents
 Metal Complexes as Photo- and Radiosensitizers
 Treatment of Wilson and Menkes Diseases
● Metalloneurochemistry
● Non-innocent ligands and radical containing complexes:
● Oxygen fixation by coordination complexes
 Vanadium & manganese complexes
 Chromium, molybdenum, tungsten complexes
 Cobalt complexes
 Heme & non-heme iron complexes and ferryl chemistry
 Copper & Nickel complexes
 Iron/Copper complexes
● Solar energy and Photochemistry:
III. References.
C. N. Verani Winter 2010 3
CHM 8090: Advanced Topics in Inorganic Chemistry This course does not use a single textbook. During the development of the topics, suggestions for
reading will be given. Some suggested sources to keep handy are as follows.
1. Miessler and Tarr, “Inorganic Chemistry”, Prentice-Hall, 3nd Ed., 2003, 720 pages
Publisher: Prentice Hall; 3rd edition ISBN: 0130354716
2. Housecroft and Sharpe, “Inorganic Chemistry” Science & Engineering Library,
3. Huheey, Keiter and Keiter "Inorganic Chemistry" 4th edition Addison-Wesley Pub Co
2000.
4. J. McCleverty: Chemistry of 1st-row transition metals, Oxford 1999.
5. B. N. Figgis & M.A. Hitchman, "Ligand Field Theory and Its Applications" Wiley-VCH
Other references will constitute of research papers published on the literature and critical reviews.
Copies of these publications can be downloaded with help of the Library’s E-journal finder list at
http://www.lib.wayne.edu/resources/journals/alphabetic/index.html
IV. Lectures.
During the lectures presentation and clarification of the contents will take place. Attending
lecture, participating, and taking notes is fundamental to succeed in the class. Questions will be
addressed during lecture and office hours will be available. You are responsible for learning the
material presented in the lectures and in missed lectures. While most material will be covered in
lectures, some material may be covered only by assigned readings.
V. Evaluation.
● 1st hour exam (20%)
● 2nd hour exam (20%)
● Microseminar on article review* (10%)
 Individual, 10-15 min talk, 3-4 slides maximum
● Seminar* (20%)
 Individual, 30-minute talk, PowerPoint presentation & questions
 Literature search can encompass one of the topics listed above and not
discussed in the classroom, the work of a particular research group, topics
related to the research interest of the student within the WSU inorganic division
(however, the work developed by Allen, Brock, Endicott, Verani, or Winter, as
well as any other WSU group are not recommended).
● Final exam (determined by the university): (30%)
* Details will be discussed accordingly
The final scores will be sorted out in groups and given an equivalent Letter Concept. If no clear
cut offs are reached, the single highest grade will be assigned as equals to 4.00 and the remaining
grades will be converted accordingly to the WSU graduation system, where 4.0 is equivalent to A, 3.67
is equivalent to A-, 3.33 is equivalent to B+, 3.0 is equivalent to B, 2.67 is equivalent to B-, 2.33 is
equivalent to C+ and 2.00 is equivalent to C. If a student misses either the 1st or the 2nd hour exam,
the lowest grade obtained in any of the three hour exams will replace the missing grade. The third
hour exam will not be replaced and the student will receive a failing grade.
VI. Academic Honesty.
C. N. Verani Winter 2010 4
CHM 8090: Advanced Topics in Inorganic Chemistry Students are expected to exhibit academic honesty and integrity at all times. Cheating on
course work or any other form of academic dishonesty is abhorrent to the academic process and will
not be tolerated under any circumstances. Cheating will not be tolerated and is likely to lead
to expulsion from the University according to the rules of the College of Arts and Science and the
Wayne State University.
VII. Attendance.
Class attendance is voluntary. Exam attendance is required. No make-up exams will be
available. If a student misses either the 1st or the 2nd hour exam, the lowest grade obtained in any of
the three hour exams will replace the missing grade. The third hour exam will not be replaced and
the student will receive a failing grade.
VIII. Office Hours and Communication Policy.
Meetings can be arranged at any convenient time by previous appointment. Communication
via email is welcomed and will be employed routinely along the course. Due to the impossibility of
easy tracking and recording, telephone calls and messages will not be answered.
C. N. Verani Winter 2010 5
CHM 8090: Advanced Topics in Inorganic Chemistry IX. Tentative Class Schedule.
Month
Week
January
11 M
13 W
15 F
18M
20W
22F
25M
27W
29F
1M
3W
5F
8M
10W
12F
15M
17W
19F
22M
24W
1F
3M
5W
8F
10M
12W
15F
17M
19W
22F
24M
26W
29F
31M
2W
5F
7M
9W
12F
13
14M
16W
19F
21M
23W
26F
Syllabus recitation + Previous course evaluation + Goals
Origin of the Elements + Research modus-operandi
Methods: Elemental Analysis
MLK day
Methods: Infrared spectroscopy, theory and instrumentation
Methods: Study cases in infrared spectroscopy
Methods: Mass spectrometry, theory and instrumentation
Methods: Study cases in mass spectrometry
Methods: X-ray diffraction and ORTEPs
Metals: Geometry and isomerism + Nomenclature
Metals: Crystal Fields & bonding
1st hour exam
Metals: Ligand Fields & bonding
Metals: Molecular Orbitals & bonding
Metals: Molecular Orbitals & bonding
Metals: 3d metals
Metals: 4d and 5d metals
Metals: Inorganic reaction mechanisms
Metals: Inorganic reaction mechanisms
Ligands: Planning and synthesis + ammines, bipy & related ligands
Ligands: Tripodal and pendant-arm ligands
Ligands: Tripodal and pendant-arm ligands + Selection of article & microseminar topic
Trends: Dioxygen activation
Trends: Dioxygen activation
article review deadline + microseminar
article review deadline + microseminar
Spring break
Spring break
Spring break
Ligands: Appended functionalities, imaging agents, and peptide bioconjugates
Ligands and trends: Bioinorganics and asymmetric synthesis
Ligands and trends: Schiff bases and metallomesogens
Ligands: Modular chemistry and magnetism
2nd hour exam
Basics on Rethoric: How to prepare a talk
Trends: Efforts toward renewable energy
Trends: Renewable energy, modular chemistry and hydrogen storage
Trends: Solar energy and water splitting + deadline literature for seminar
Trends: Solar energy and water splitting
seminar presentation from 12:30 pm to ~4:30 pm
Ligands: Macrocycles, cages, and more
Ligands: Macrocycles, cages, and more
Ligands: Electroactive or non-innocent ligands
Methods: Electrochemistry, theory and instrumentation
Methods: Study cases in electrochemistry
Ligands and Methods: Fused ligands and electrochemistry
28M
30W
3rd hour exam (possible day)
3rd hour exam (possible day)
February
March
April
Saturday
C. N. Verani Activity
Winter 2010 6
CHM 8090: Advanced Topics in Inorganic Chemistry The following class schedule is tentative and subject to change.
C. N. Verani Winter 2010 7