Daily Board Lists
for Chem 4380
Fall 2007
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Wed Dec 12 Comprehensive Final Exam 8:00 – 10:00 am
Fri
Dec 7
Reading Day (no lecture). Office hours in place of lecture time. Updated final exam review sheet is now posted.
Wed
Dec 5
organometallics literature study (bonus) due in lecture
Four common transformations
1. oxidative addition
2. reductive elimination
3. beta hydrogen elimination
4. alkyl or hydride migration
Catalytic cycles
Mon
Dec 3
h hapticity
CO as a ligand, p 546
bent vs linear nitrosyl Organometallics 2007, 26, p 4881. Cp*W(NO)(PR3)
Fri Nov 30
Labile vs inert p 546
Organometallic chemistry
EAN Rule
Ligand electron counting practice
Read Sec. 21.1 – 21.12, 18, 23 – 25.
As mentioned on Wed, we will have a final (bonus) literature
study. Those of you who have obtained full
credit on all literature studies may choose to opt out of this activity. No bonus beyond the maximum available will be
offered. The assignment requires you to
use one of the following three ACS journals: 2007 J. Am. Chem., Inorg. Chem. or Organometallics.
You must find one example of a formally 18 electron compound (EAN rule)
and one separate example of a 16 electron compound. These can be from the same or separate
articles. For each complex you must show
the metal charge, its dn
electron count, ligand charges, and the electron counting scheme you used to
arrive at your EAN value. Also provide
article citations and DOI’s for me to cross
check your articles. Due on Wed Dec 5.
Wed
Nov 28
FOURTH EXAM Ch 5,8,19,20 as
assigned
Mon
Nov 26
thermodynamics
Kf
chelate, macrocyclic effect
Read: Sec. 20.1 – 20.3, 20.5
Work: Exercises 20.1 – 5, 7, 15, Problems 20.1,2
Wed, Fri Nov 21,23 THANKSGIVING
BREAK
Mon
Nov 19
meff (spin only, L & S)
Read: Sec. 20.1 – 20.3
Work: Exercises 20.1 – 5, 7, 15, Problems 20.1,2
Fri
Nov 16
spec series: pi bases < sigma only < pi acids
Electronic,
MO pictures of Td, Oh, D4h develop an MO
diagram for a simple ML4 complex with D4h symmetry.
Magnetism
meff (spin only, L & S)
diamagnetic, paramagnetic, ferromagnetic
Work: Exercises 19.1 – 19.9, 19, 25 Problems 19.1 – 19.3
Read: 19.1 – 2, 19.4 - 6
Wed
Nov 14
Ligand field splittings Td, Oh, D4h
LFSE high spin, low spin
example p 465
spec series: pi bases < sigma only < pi acids
Electronic,
MO pictures of Td, Oh, D4h
As homework: develop an MO diagram for a simple ML4 complex with D4h symmetry.
Work: Exercises 19.1 – 19.9, 19, 25 Problems 19.1 – 19.3
Read: 19.1 – 2, 19.4 - 6
Revised essays due. Maximum allowable
points will be half of the total points missed.
In addition to your rewritten essay, also include your original
marked-up submission for comparison.
Mon
Nov 12
Quiz 8 coordination
complexes (Sec
8.1 – 8.5, Exercises 8.1 – 8.4, 8.7 – 8.11)
Literature Study #
3 due first thing
CN = 5
Some practice Problems 8.1 – 8.9
ligand field theory
spectrochemical series 1. L effects 2. M effects
Read: Ch 19
Work: Exercises 8.1 – 8.15, Problems 8.1 – 8.9
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Fri Nov 9
Jahn-Teller
Isomerism: cis, trans
mer, fac, optical
CN = 4 Td, D2d, D4h
Problem 8.6 p 236
CN = 5 C4v, D3h
Read: Ch 8
Work: Exercises 8.1 – 8.15, Problems 8.1 – 8.9
Literature study #3 (Due Monday Nov 12)
Using the 2007 primary literature, find one example each of a 4 coordinate tetrahedral metal complex, a 4 coordinate square planar metal complex, and a 6 coordinate octahedral metal complex. Here the labels loosely refer to pseudo Td, D4h, and Oh systems. Your complexes need not have rigid symmetry. For each complex you must identify the metal charge and dn count as well as the charge(s) on the coordinated ligands. These can come from different articles or the same article. As in the past provide complete citations of any articles used
Wed
Nov 7
M-ligand adducts, complexes
M, L characteristics
common ligands to know p 226
CN = 6 Oh, trigonal prism p 224
common Oh distortions, d orbital splittings
bite angle, Jahn-Teller distortions
Read: Ch 8
Work: Exercises 8.1 – 8.15, Problems 8.1 – 8.9
Mon
Nov 5
Kinetics issues and redox
inner, outer, complex
atom transfer processes
oxidative addition, reductive elimination
Marcus equation (see poster to the left of the elevator on the 2nd floor and p 517 in text)
Read: Sec. 5.10 – 5.12, 5.17, Read Sec 8.1 – 8.5 before Wed
Work: Exercises 1 – 10, 13, Problems 1,4,5,7,8,10,11,12
Fri
Nov 2
Second essay due
first thing in lecture
Latimer diagrams 1. balanced half reaction
2. disproportionation
3. pH effects
Frost: examples used in class p 156, 361, 167, 416, 382, 438, 582
Water electrolysis p 403
Read: Sec. 5.10 – 5.12
Work: Exercises 1 – 10, 13, Problems 1,4,5,7,8
Wed Oct 31
Quiz 7 in class
dissolving gold with cyanide and air
ligand features and redox (softness and p 532, 534)
Latimer diagrams 1. balanced half reaction
2. disproportionation
3. pH effects
Read: Sec. 5.10 – 5.12
Work: Exercises 1 – 10, 13, Problems 1,4,5,7,8
Mon
Oct 29 Transition metal complex writeup is due on Tues
Quiz 6 due first
thing (Questions 8 and 9 on the redox review sheet).
Nernst equation
Complexation effects
Aqua Regia, cyanide and gold
Read: Sec. 5.1 – 5.9
Work: Exercises 1 – 5, Problems 1,4,8
Friday Oct 26 This is the final day for me to receive drafts of your essays to read and critique in advance of Monday’s deadline.
PT quiz This time the whole table (s, p, d blocks, not the f block)
Student review practice Sec 5.1 – 5.4 Some of you will be performing demos to illustrate your practice questions.
Wed Oct 24
Third Exam Chapters 3 and 4
Mon
Oct 22
Amphoterism of Al2O3
Aqueous cations and an ionic model
Carbonic anhydrase, Zn example p 736
Lewis acids and bases induction, resonance, sterics
Hard/soft acids and bases (see also section 1.9(e) p 32)
B, P, S family examples
Read: Sec. 4.1 – 4.5, 4.7 – 4.10
Work: Exercises 4.2 – 4, 6,7,10-14,18-24,26,27,29,31-33. Problems 4.1 – 3, 5,6,11,12
Fri
Oct 19 FALL BREAK (much deserved for all)
Wed Oct 17 The second and final essay of the semester is posted and due Friday Nov 2 (different from syllabus posted date)
Quiz 5 Haber cycles and
lattice enthalpies
Bronsted acids and bases
Solvent leveling p 117
Oxoacids p 120
Oxides p 123,
Amphoterism of Al2O3
Read: Sec. 4.1 – 4.5, 4.7 – 4.10
Work: Exercises 4.2 – 4, 6,7,10-14,18-24,26,27,29,31-33. Problems 4.1 – 3, 5,6,11,12
Mon
Oct 15 A day behind on the
syllabus
Student
review practice Sec 4.1 – 4.2
Second literature
study due (described
on front page of the syllabus). Focus on
the use of symmetry in choosing your example.
Be certain that your summary clearly explains how symmetry from Ch 3 is
illustrated in the article. Send either
the DOI link or a copy of the article for me to check.
Fri
Oct 12
Final PT quiz This time the whole table (s, p, d blocks, not the f block)
Energetics of solids Haber cycle Here are my worked Haber problems from the text.
Born-Mayer
solubility, thermal stability of solids
Read: Sec. 3.1 – 3.16
Work: Exercises 3.1 – 3.7, 3.9 -11,13,14,16-18 Prob 3.3 – 3.8, 10 – 12, 16
Wed
Oct 10
Quiz 4 solids (pure metals
only)
Ionic lattices
Read: Sec. 3.1 – 3.16
Work: Exercises 3.1 – 3.7, 3.9 -11,13,14,16-18 Prob 3.3 – 3.8, 10 – 12, 16
To further answer the request for notes. All of the figures shown in lecture today were drawn right from the text (pages numbers provided). My assumption, therefore, is that you are looking at the figures in the text. It has always been my expectation that you daily bring your text to lecture, you were required to buy it, so it is incumbent on me to show you how we use it. If you choose not to bring your text or ever use it, that is your choice, of course. When a particularly busy figure is used (that is not in the text) you know that these are provided to you as they were for the perovskite mineral in today’s handouts.
Chem 3150 lab students: The following pairs of complexes are assigned. These will the focus of your lab work during this rotation.
Two student groups (listed below) need to make additional batches of two of the solids. These procedures were provided in lecture. To maximize lab time, I’ll need you to get to lab about 30 min earlier on Tues. The synthetic materials will be ready for you. Everyone else will walk into lab on Tues ready to make 5 mL of a 0.01 M solution of their complex. Consult the www posted instructions for full formulas of your complexes.
Rachel, Michelle Ni(en)3+2 Co(en)3+3
Lindsay, David Co(NH3)6+3 Co(en)3+3
Thi, Ariel, Chris Co(NH3)6+3 Co(NH3)5Cl+2 You will need to make an additional batch of [Co(NH3)6]Cl3. The procedure is provided in lecture.
Josh, Leah Co(en)3+3 Cr(en)3+3 You will need to make an additional
batch of [Co(en)3]Cl3.
The procedure is provided in lecture.
Mon
Oct 8 The second
and final essay of the semester is posted and due Friday Nov 2 (different
from syllabus posted date)
W radius 1. relative radius and coord number p 24 W radius work
2. radius ratio and coord number p 80
hcp p 75
Holes: Td, Oh p76
Ionic lattices
Read: Sec. 3.1 – 3.7
Work: Exercises 3.1 – 3.7, 3.9 – 3.11 Prob 3.3 – 3.6
Fri
Oct 5 See this invite for a visit to Oakridge National Labs in
late October
Periodic Table quiz: transition metals
Why solids
Unit cells
packing of spheres As an exercise, calculate the percentage of filled space (packing efficiency) in a P, I, and F unit cell.
P, I, F
closest packing ccp, hcp
Read: Sec. 3.1 – 3.7
Work: Exercises 3.1 – 3.7
Wed Oct 3
Second Exam Chapters 2 and 7 you will be given the point group symmetry
flow chart
any character tables, and SALC sketches
Mon
Oct 1 3 p
office time canceled today
H2O, BH3
Transition
metal complexes Oh,
Td
benzene and cyclopentadiene examples
Practice exams 2 and 3 (no Acid /base) are representative of the questions you will face on Wed.
Read: Sec 7.1 – 7.8
Work: Exercises 7.1 – 7.7, 7.10, Prob 7.1-3, 7.6-7.10
Fri
Sep 28
Periodic Table Quiz d-block elements
Revised PT essay due
AO symmetry from point group Hook’s Law addendum to Wed notes for vibrational spectroscopy and N2.
Symmetry and bonding new
SALC’s pp 792
Examples: NH3 ( and
p 64) , H2O, BH3
Read: Sec 7.1 – 7.8
Work: Exercises 7.1 – 7.7, 7.10, Prob 7.1-3, 7.6-7.10
Wed
Sep 26 Vanderbilt wants you
for grad school. See
this invite for an expense-paid visit in October.
chirality, spectroscopy
SALC’s
MO’s and symmetry Color pictures of H2O and NH3 MO’s.
revisit the end of Chapter 2
Read: Sec 7.1 – 7.8
Work: Exercises 7.1 – 7.7, 7.10, Prob 7.1-3, 7.6-7.10
Mon
Sep 24
Quiz 3 Symmetry
Character tables p 786
Applications: polarity, chirality, spectroscopy
Read: Sec 7.1 – 7.8
Work: Exercises 7.1 – 7.7, 7.10, Prob 7.1-3, 7.6-7.10
Effective writing is an iterative process. I am returning your first iteration. Strengths in the better essays were original examples, accurate and effective analogies, effective use of figures, demonstration of how chemists use the organization of the PT to explain real world properties, relation of the PT structure to atomic structure (function follows from structure) and inclusion of good real world examples. Weaknesses in some essays included aiming at too high of an audience and using technical details that would quickly be lost by an educated non-chemist. These were a distraction. Weaknesses included missing an obvious connection to all elements-- the inertness of the noble gases, and how this is a governing principle in the organization of the PT. Another weakness was not using a real world example to make your point (for the stronger essays this was done more effectively). Some essays did not mention an actual compound until the 2nd to the last paragraph. At this point the reader would have lost interest. This should come early and be a unifying theme throughout the essay.
Carefully consider my comments. See me during office time to discuss them and ways you can improve. I will accept on Friday revised essays (also include your original marked-up copy for comparison). Your revision may earn you a maximum of up to half of the points you missed. Therefore, a significantly improved original draft that earned 39/50 could become 45/50 (6 more out of the original 11 points lost) upon revision.
Fri Sep 21
Periodic table
essay due
Periodic Table Quiz Maingroups
again at my office today/
Sn and we don’t mean tin
Point group symmetries p 199 flow chart
Read: Sec 7.1 – 7.5
Work: Exercises 7.1 – 7.7, Prob 7.1
Clearly symmetry is a visual thing. Visual representations of molecules is a tool you should carry over from Organic chemistry. Practice symmetry until you are comfortable. Remember, the pictures we draw are on 2-D paper, but symmetry is a 3-D idea.
Wed
Sep 19
Symmetry operations
Symmetry elements: E, Cn, i, Sn, s
Point group symmetries Here is a link to some symmetry practice.
Read: Sec 7.1 – 7.3,
Work: Exercises 7.1 – 7.7, Prob 7.1
Comments about the essays. Remember that the instructions call for you to use the blank periodic table as one of your figures in your essay. Use as many other figures as you like, but this one is a minimum requirement. It is on p 2 of the pdf instruction file and can be easily copied using the image copy tool of Adobe. Avoid listing series of periodic trends in your essay; you don’t have enough space to flesh these out as would be required for clarity. Try to hear yourself saying that if you are a non-chemist. That is the kind of thing that drives people away from chemistry. Remember your goal is try and draw people into a better appreciation for why we chemists have and use the periodic table.
Mon
Sep 17
First Exam Chapters 1 and 2
Fri
Sep 14 No PT quiz today (we will begin
d block next week)
Hb-O2 p 728
heteronuclear diatomics: NO, CO, HF
even ionic bonding can be explained
Heteronuclear examples
3c,2e bonds, bridging hydrides, agostic interactions
Periodic Table Essay due in one week
Read: Sec. 2.1- 2.11
Work: Exercises 2.1 – 2.20, Prob 2.1 – 2.2, 2.4, 2.8
Wed
Sep 12
H2 and excited states
X2 diatomics pp 56 Cl2 bond strength
applications: N2 fixation, Hb-O2 p 728 The frequencies I gave for O2n‑ on the handout in class were oxygen-oxygen stretching frequencies.
PES p 185
Here is my answer for the the O2 MO’s with charge.
Read: Sec. 2.1- 2.11
Work: Exercises 2.1 – 2.20, Prob 2.1 – 2.2, 2.4
Comments about Quiz #2. Question 1: Most hit correctly on the +2 charge common to both Cd2+ and Ca2+, but there must be something more. Consider that Mg2+ and Ca2+ both have the same charge, but that they are quite different in living systems. The same is true of Zn2+. There must be something more. It is reasonable to consider that Cd2+ is comparable in size to Ca2+ given that the extra 4d10 electrons of Cd2+ are pulled in tightly because of its high Zeff.
Question 2: It appears that some are not using the systematic approach to do dot structures and shape that were introduced in general chemistry. Rather, it appears people are relying on their instincts from organic chemistry, which is fine for carbon, but they don’t work for xenon or many other main group compounds. Use the gen chem system and review it before the exam. See me with questions.
