Download Chem 3820 Outline - U of L Class Index

Chemistry 3820: Transition Metal Chemistry
Fall 2006
Instructor: Dr. Paul G. Hayes
Contact Information: Office: E870 (University Hall)
E- mail: [email protected] (preferred)
URL: http://people.uleth.ca/~p.hayes/
Phone: (403) 329-2313
Office Hours: 10:00 – 11:00 MWF (or by appointment)
Class URL: http://classes.uleth.ca/200603/chem3820a/
Credit Hours: 3.0
Prerequisites: Chemistry 2600, 2720, 2810
Course Subject: The properties, structures, and reactions of inorganic compounds with an
emphasis on transition metal chemistry.
Lectures: MWF at 9:00-9:50 in C620
Labs: W at 13:00-15:50 in D770. The laboratory portion of the course commences on
September 13 with an introduction and check- in. The details of laboratory policies and operation
will be addressed at that time. The laboratory manual will be distributed via e- mail (.pdf
format). It is imperative reading – it contains information pertinent to the laboratory which you
must read and respond to. It is a requirement that all students wear a lab coat, safety glasses
(contact lenses beneath safety glasses are not acceptable) and adequate footwear (sandals are not
permitted). A deposit of $15.00 is required in order to obtain a locker key. Please pay at the
cashier’s office and bring the token to the laboratory. Refer to the lab manual for complete
details on these and other topics relating to the laboratory component of Chemistry 3820.
Exams: Midterm - October 6 and November 17 (tentative).
Final – Saturday, December 16 (9:00-12:00; tentative)
Recommended Text Book:
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D. W. Shriver, P. W. Atkins, Inorganic Chemistry, 4th Ed., Freeman, New York, 2006.
ISBN: 0716748789, [QD151.5 S57]. (Note: 3rd Ed. is completely acceptable).
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Previous editions may be used, but may lead to inconvenience due to material rearrangement.
Chemistry 3820 (Fall 2006)
Additional Useful References:
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A. F. Hollema nn, E. Wiberg, Inorganic Chemistry, Academic Press, San Diego, 2001.
ISBN: 0123526515, [QD 151.3 W5313 2001].
G. L. Miessler, D. A. Tarr, Inorganic Chemistry, 3rd Ed., Prentice Hall, Upper Saddle River,
NJ, 2004. ISBN : 0130354716, [QD 151.3 M54 2004].
J. E. Huheey, E. A. Keiter, R. L. Keiter, Inorganic Chemistry: Principles of Structure and
Reactivity, 4th Ed., HarperCollins, New York, 1993. ISBN : 006042995X, [QD 151.2 H84
1984].
F. A. Cotton, G. Wilkinson, P. L. Gauss, Basic Inorganic Chemistry, 3rd Ed., Wiley, New
York, 1995. ISBN : 0471505323, [QD 151.2 C691 1995].
F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann, Advanced Inorganic Chemistry,
6th Ed., Wiley, New York, 1999. ISBN : 0471199575, [QD 151.2 H84 1984].
C. E. Housecroft, A. G. Sharpe, Inorganic Chemistry, 2nd Ed., Pearson Education, Harlow,
2004. ISBN: 0130399132, [QD 151.2 H68 2005].
N. N. Greenwood, A. Earnshaw, Chemistry of the Elements, 2nd Ed., ButterworthHeinemann, Burlington, 2002. ISBN: 0750633654, [QD 466 G74 1997].
Course Contents (may be subject to change):
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General introduction to transition metal chemistry (including nomenclature).
Coordination complexes.
Molecular symmetry and group theory.
Crystal field (CF) theory.
Molecular orbital (MO) theory for transition metal complexes (ligand field theory).
CF or MO theory to explain magnetism and UV-Visible absorption and emission spectra.
Reactivity: thermodynamics
Reactivity: kinetics and reaction mechanisms
Special topics (time permitting; e.g. organometallic chemistry, catalysis, etc.)
Evaluation Mechanisms :
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2 Midterms (30%; 15% each)
1 Final exam (40%)
Class Participation & Quizzes (10%)
Laboratory (20%). Note: All experiments must be performed (and submitted before the end of
the course) in order to pass.
© 2006 - Dr. Paul G. Hayes – University of Lethbridge
Chemistry 3820 (Fall 2006)
Course contents in more detail (may be subject to change):
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1. General Introduction to Transition Metal Chemistry
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Position of the transition metals and lanthanides in the periodic table, definitions of common
terms.
Physical properties, basic chemical properties, oxidation state trends (Frost diagrams),
occurrence, some applications.
Electronic configuration for metals and complexes.
Review of quantum numbers (n, l, ml, ms) , effective nuclear charge, radial distribution
functions for s-, p-, d- and f-orbitals, shapes of the d- and f-orbitals.
General trends: atomic radii, ionic radii, ionization energies.
2. Coordination Complexes
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History – Werner vs Blomstrand, definitions of common terms and IUPAC nomenclature.
Coordination number and geometry.
Types of ligand: bridging and chelating (monodentate, bidentate, polydentate etc.).
Types of isomer: geometric (cis, trans, mer, fac), optical, ionization, linkage, coordination,
‘polymerization’. Isomerization in 4-, 5- and 6-coordinate complexes.
3. Molecular Symmetry and Group Theory
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Systematic classification of molecules into point groups
Reproducible representations, irreducible representations and character tables
Applications to chemical bonding, with a particular emphasis on construction of MO
correlation diagrams.
4. Crystal Field (CF) Theory
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Crystalline lattices – how crystal field theory came about.
Octahedral CF splitting diagram.
Crystal field splitting energy (CFSE), spectrochemical series for both ligands and metals.
Low spin and high spin complexes
Jahn-Teller theory, square planar geometry.
Tetrahedral complexes, tetrahedral versus octahedral geometry (octahedral site preference
energy).
5. Molecular Orbital (MO) Theory for Transition Metal Complexes (Ligand Field Theory)
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Recap – MO diagrams for simple organic molecules (H2 , HF, N2 , O2 , CO, H2 O, NH3 ).
Constructing MO diagrams for octahedral and tetrahedral complexes (considering σbonding only) – symmetry of valence s-, p- and d-orbitals, linear combinations of ligand
orbitals.
Incorporating π-interactions à explanation for spectrochemical series of ligands.
© 2006 - Dr. Paul G. Hayes – University of Lethbridge
Chemistry 3820 (Fall 2006)
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6. CF or MO theory to explain magnetism and UV-Visible absorption / emission spectra
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Magnetism: paramagnetism, diamagnetism, magnetic susceptibility, χ vs T, measuring
magnetic susceptibility, ferromagnetism, antiferromagnetism, ferrimagnetism.
UV-Visible absorption spectra: (a) position and number of transitions: d1 complexes, d2
complexes, Tanabe-Sugano diagrams, microstates, mL vs mS tables, terms, transitions
between terms, assigning the ground state term, Racah parameters (A, B and C) to assign
relative energies to all the terms, metal ions in the gas phase vs metal complexes, correlation
diagrams, the principal Racah parameter (B), back to Tanabe-Sunago diagr ams (E/B vs
∆o/B), non-crossing rule, high spin to low spin transitions, nephelauxetic effect; (b)
intensities of transitions: forbidden transitions, spin and parity (Laporte) selection rules,
vibronic coupling; (c) MLCT and LMCT bands, solvatachromism.
Luminescence, fluorescence, phosphorescence, lasers.
7. Reactivity: Thermodynamics
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Thermodynamics: equilibrium constants, formation constants {stepwise (K), overall (β)},
chelate and macrocycle effects, hard/soft acid/base theory, Irving-Williams Series.
8. Reactivity: Kinetics and Reaction Mechanisms
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Substitution reactions : (a) Kinetics, ∆S‡ , ∆V‡ , types of reaction mechanism (A, D, Ia, I d), (b)
square planar complexes, the trans-effect (A mech), (c) octahedral complexes, A vs D
mechanism, Taube’s rules (D mech) à ‘inert’ and ‘labile’ complexes, (d) exceptions.
Photochemical substitution reactions.
Electron transfer.
Most important sections in Shriver & Atkins (3rd Edition):
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Chapter 1, pg. 3-34, Atomic structure
Chapter 7, pg. 211-249, d-Metal complexes
Part of Chapter 9, pg. 291-309, General properties of the d-block metals
Chapter 13, pg. 437-464, The electronic spectra of metal complexes
Chapter 14, pg. 467-496, Reaction mechanisms of d- metal complexes.
Chapter 16, pg. 537-581, d- and f-Block organometallic complexes
Parts of Chapters 2 (e.g. structures of simple solids), 3 (e.g. MO diagrams for N2 and CO), 4
(e.g. molecular symmetry, point groups, character tables), 5 (e.g. hard and soft acids and
bases), and 6 (e.g. metal extraction, oxidation and reduction).
Chapter 17, pg. 583-613, Catalysis
© 2006 - Dr. Paul G. Hayes – University of Lethbridge
Chemistry 3820 (Fall 2006)
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Tentative Course Schedule
Monday
Wednesday
Friday
Lab
Sept. 6
Sept. 8
Sept. 8
No Lab period
Sept. 11
Last class before
add/drop deadline
(Sept. 12)
Sept. 18
Sept. 13
Sept. 15
Sept. 13
Lab Introduction &
Check- in
Sept. 20
Sept. 22
Sept. 20
Spectroscopy
Lecture/Demonstration
Sept. 25
Sept. 27
Sept. 29
Library Info Session
L1170A
Sept. 27
Spectroscopy
Lecture/Demonstration
Oct. 2
Oct. 4
Oct. 6
Midterm Exam #1
Oct. 4
Spectroscopy
Lecture/Demonstration
Oct. 9
Thanksgiving – No
class
Oct. 11
Oct. 13
Oct. 11
Oct. 16
Oct. 18
LS1a
Oct. 20
Oct. 18
LS1b
Oct. 23
Oct. 25
Oct. 27
Oct. 25
LS2a
Oct. 30
Nov. 1
Nov. 3
Nov. 1
LS2b
Nov. 6
Nov. 8
Nov. 10
Last Class before
Withdrawal deadline
(Nov. 9)
Nov. 8
© 2006 - Dr. Paul G. Hayes – University of Lethbridge
LS3a
Chemistry 3820 (Fall 2006)
Nov. 13
Remembrance Day –
No Classes
Nov. 15
Nov. 20
Nov. 22
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Nov. 17
Midterm Exam #2
Nov. 15
Nov. 24
Nov. 22
LS3b
LS4a
Nov. 27
Nov. 29
Dec. 1
Nov. 29
LS4b
Dec. 4
Dec. 6
Dec. 8
Last day of Class
Dec. 6
Lab cleanup &
checkout
Dec. 16 (Saturday)
Final Exam (9 – 12)
© 2006 - Dr. Paul G. Hayes – University of Lethbridge