Professional Documents
Culture Documents
The schedule below will be updated with notes, figures, and readings from
lectures.
*The wrl files require a VRML viewer. Cosmoplayer is one that works with
netscape and internet explorer.
Symmetry PDF
1 2/6/02 Elements and CCC 3.1-3.2
Operations WRL*
PDF 3.5-3.6,
3 2/11/02 Character Tables CCC
Appendix 3
IR Spectroscopy PDF
4 2/13/02 CCC 3.7-3.8
and Symmetry
15.1-15.4,
Group 16 PDF
9 02/25/02 CCC 15.7-15.8,
bonding
15.10
Intro to
10 02/27/02 Coordination CCC PDF Ch. 19
Chemistry
Lectures
11 03/01/02 Exam #1 CCC 1-9 and
Readings
Crystal Field PDF
12 03/04/02 CCC 20.1-20.3
Theory
Pi-donor/acceptor PDF
13 03/06/02 CCC 20.4
MO's
Electronic PDF
14 03/08/02 CCC 20.5-20.6
Spectra
Orgel and
15 03/11/02 Tanabe-Sugano CCC PDF 20.6
diagrams
Magnetic
16 03/13/02 Properties of CCC PDF 20.8
Coord. compds.
Ligand
Subsitution:
17 03/15/02 CCC PDF 25.1-25.3
Square Planar
Complexes
Ligand
Substitution: PDF
18 03/18/02 CCC 25.4
Octahedral
Complexes
Alkyls of Groups
21 04/01/02 1, 2, 12, 13, and RRS PDF 18.1-18.5
14
Transition metal
PDF 23.2-23.3,
22 04/03/02 alkyls and RRS
23.7, 23.9
hydrides
PDF
ηx-ligands and
24 04/08/02 fluxional RRS Ferrocene 23.13-23.15
processes MO's
Homogeneous PDF
28 04/19/02 RRS 26.1-26.3
catalysis
Homogeneous PDF
29 04/22/02 RRS 26.1-26.3
catalysis
30 04/24/02 Exam #3 in class RRS
Metals in PDF
33 05/01/02 RRS 28.1-28.5
Biology
Metals in PDF
34 05/03/02 RRS 28.1-28.5
Biology
Metals in PDF
35 05/06/02 RRS 28.1-28.5
Biology
Solid State PDF
5.1-5.11,
36 05/08/02 RRS
Chemistry 5.17
Department of Chemistry
Send comments and suggestions to course webmaster: ahock@mit.edu
Last updated: May 7, 2002
Prof. Christopher C.
Cummins
Prof. Richard R.
Schrock
---
Welcome to 5.03.
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Department of Chemistry
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Last updated: February 13, 2002
Initial concept by Tet Matsuguchi
Announcements
05/07/02: Course Evaluations will be held this Friday,
5/10/02.
05/01/02: The product 1(e) of pset 7 should be acetic acid
(CH3COOH)
05/01/02: The syllabus has been updated for the remainder
of the semester.
04/29/02: The average of exam 3 was 72.7 +/- 18.
04/29/02: Pset 7 is up. Be advised that it is due FRIDAY in
class
04/23/02: PS 5 will be in the chem ed office as of 8:30 am or
so. Please be SURE you are picking up only your own pset.
Thank you.
04/22/02: keys to PS 5 & 6 have been uploaded. Also, please
note that lecture 27,28, and 29 are up and that 27 was
incorrectly iin 28's place. Everything is correct now, though.
Happy studying!
04/21/02: This link has been added to the resorces page, and
you may find it useful.
04/21/02: There will be a review session for exam 3 on
Tuesday the 23rd at 1:00 in room 1-134
04/21/02: The MO's of ferrocene have been posted on the
notes page.
04/08/02: Please note: Problem 3f of pset#5 should have a
4:1 ratio of H's
03/30/02: Welcome back! We hope everyone had a
wonderful spring break.
03/30/02: pset #5 is up!
03/30/02: The syllabus, calender, and assignments have been
updated with information about the second half of the
semester. -Adam
03/18/02: Adam and Amrit will have extra office hours tues
from 5:30 to 7:30 pm in 1-375 -Adam
03/18/02: Soln's to pset #4 are up!
03/18/02: EXAM 2 will be in 2-190 on Wed 03/20/02 at
7:30 pm! -Adam
03/14/02: Several changes were made to pset #4's
instructions. Please download the new pdf, the file name is
pset4b.pdf -Adam
03/13/02: Please photocopy pset #4 if you want to study for
the exam from your work. The solutions will be posted the
afternoon the pset is due, but it will most likely not be
returned in time for you to study for the test. -Adam
03/13/02: pset #3 solutions are up!
03/12/02: pset 4 is up.
03/11/02: Prof. Cummins will have extra office hours this
week R 3-4 and F 11-12. -Adam
03/05/02: FYI, the avg +/- SD for pset 1, 2, and the exam
were:
pset1: 39 +/- 8
pset2: 29 +/- 9.6
Exam1: 47 +/- 13
Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments |
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Department of Chemistry
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Last updated: May 7, 2002
Teaching Assistants
Administration:
Kris Grabarek, Assistant
Director of Chem. Education,
Room 2-204, x3-0909,
grabarek@mit.edu
Laura Howe, Web Manager,
Room 2-204, x8-7492,
lhowe@mit.edu
Jennifer Picray, Course
Manager, Room 2-204, x3-7271,
jlpicray@mit.edu
Textbook: Inorganic Chemistry,
Housecroft and Sharpe (Prentice Hall,
2001) ISBN 0582-31080-6
Other books that may prove useful (on
reserve in 14N-132):
Recitations Recitation sections are
assigned by the registrar. Changes to
assigned recitations will be made in the
Chemistry Education Office (in person
only, no changes will be made by phone
or e-mail).
Academic Honesty
It is expected that students will maintain
the highest standards of academic
honesty.
With respect to homework assignments,
it is expected that no student will turn in
work that is not his or her own. Copying
of other students work is not permitted.
Full credit will not be awarded for
answers only: remember to show your
work! Illegible, messy, or
difficult-to-decipher work will not be
graded. Copy over your work prior to
turning it in if necessary.
It is expected that during a test or
examination, a student will not (1) accept
or use information of any kind from other
students; (2) represent the work of
another student as his or her own; (3) use
aids to memory other than those
expressly permitted by the examiner.
Following a test or examination, a
student will not try to deceive teachers or
graders by misrepresenting or altering his
or her previous work. In advance of a test
or exam, a student will not knowingly
obtain access to the exam questions.
Departures from the above standards are
contrary to fundamental principles of
MIT and of the larger scientific
community. Such departures are
considered serious offenses for which
disciplinary penalties, including
suspension and expulsion, can be
imposed.
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Department of Chemistry
Send comments and suggestions to course webmaster: ahock@mit.edu
Last updated: February 6, 2002
Instructors:
Prof. ccummins@mit.edu
Christopher
2-227 x3-5332 Office Hours: 3-4
C.
TW in 2-227
Cummins
Prof.
Richard R. 6-331 x3-1596 rrs@mit.edu
Schrock
Amritanshu
asinha@mit.edu R 5-6 2-131
Sinha
Recitations:
1 W9 2-139 Adam
2 R2 2-132 Amrit
3 R1 1-134 Adam
4 T1 1-134 Amrit
Administration:
Kris Grabarek, Assistant Director of
Chem. Education, Room 2-204,
x3-0909, grabarek@mit.edu
Laura Howe, Web Manager, Room
2-204, x8-7492, lhowe@mit.edu
Jennifer Picray, Course Manager, Room
2-204, x3-7271, jlpicray@mit.edu
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Department of Chemistry
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Last updated: February 19, 2002
Course Calendar
February, 2002
Monday Tuesday Wednesday Thursday Friday
1
4 5 6 7 8
Registration Lecture 1 Lecture 2
Day Symmetry Point Group
Elements Assignments
and
Operations
11 12 13 14 15
Lecture 3 Lecture 4 Lecture 5
Character IR LGO's and
Tables Spectroscopy MO's
and
Symmetry Problem Set
#1 Due in
class
18 President's 19 20 21 22
Day Lecture 6 Lecture 7 Lecture 8
Simple Boron N and P
MO's Hydride oxides PDF
BondingPDF
PDF
Monday
Schedule
25 26 27 28
Lecture 9 Lecture 10
Group 16 Intro to
bondingPDF Coordination
Chemistry
Problem Set PDF
#2 Due in
class
March, 2002
Monday Tuesday Wednesday Thursday Friday
1
Lecture 11
Exam #1 in
class Room
TBA
4 5 6 7 8
Lecture 12 Lecture 13 Lecture 14
Crystal Field Pi-donor/acceptor Electronic
Theory PDF MO's PDF Spectra
PDF
Add Date
11 12 13 14 15
Lecture 15 Lecture 16 Lecture 17
Orgel and Magnetic Ligand
Tanabe-Sugano Properties of Subsitution:
diagrams PDF Coord. compds. Square
PDF Planar
Problem Set #3 Complexes
Due in class PDF
18 19 20 21 22
Lecture Ligand Lecture 19 Lecture 20
Substitution: Electron Transfer
Octahedral PDF Cancelled
Complexes due to the
PDF Exam #2 exam 3/20.
Evening Exam
Problem Set #4 7:30 PM in 2-190
Due in class
25 Spring 26 27 28 29
Break Week
April, 2002
Monday Tuesday Wednesday Thursday Friday
1 2 3 4 5
Lecture 21 Lecture 22 Lecture 23
Alkyls of Transition ηx-ligands
Groups 1, 2, metal alkyls PDF
12, 13, and 14 and hydrides
PDF PDF
8 9 10 11 12
Lecture 24 Lecture 25 Lecture 26
ηx-ligands Metal Multiple
and fluxional carbonyls metal-ligand
processes and clusters and
PDF PDF metal-metal
bonds PDF
Problem Set
#5 Due in
class
15 Patriot's 16 17 18 19
Day Holiday Patriot's Lecture 27 Lecture 28
Day Reactions at Homogeneous
Holiday a transition catalysis PDF
metal center
PDF
22 23 24 25 26
Lecture 29 Lecture 30 Drop Date Lecture 31
Homogeneous Catalysis PDF
catalysis PDF Exam #3 in
class
Problem Set
#6 Due in
class
29 30
Lecture 32
Catalysis PDF
May, 2002
Monday Tuesday Wednesday Thursday Friday
1 2 3
Lecture 33 Lecture 34
Metals in Metals in
Biology Biology
PDF PDF
Problem Set
#7 Due in
class
6 7 8 9 10
Lecture 35 Lecture 36 Lecture 37
Metals in Solid State Solid State
Biology Chemistry Chemistry
PDF PDF
Problem Set
#8 Due in
class
13 14 15 16 17
Lecture 38 Lecture 39
Lanthanides Nuclear
and Chemistry
Actinides
20 21 22 23 Final 24
Exam
9:00 AM in
2-190
27 28 29 30 31
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Resources
Department of Chemistry
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Last updated: May 1, 2002
Problem
Due Solutions
Set
PDF
4 PDF* 03/18/02 fixed pg
3
7 PDF 05/03/02
8 PDF 05/10/02
* updated!!
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Department of Chemistry
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Last updated: May 6, 2002
Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources
Department of Chemistry
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Last updated: April 4, 2002
Getting Textbooks
Textbooks are available at several
bookstores on-line as well as at the
COOP.
Getting Help
Tutoring is available from the Tutoring
Services Room (TSR) of the Office of
Minority Education. Call TSR at x3-8406
any day after 2pm.
Chemistry Sites:
Organometallic Hypertextbook - The
name speaks for itself.
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Interested in Chemistry? Join
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MIT Chemistry Department
Department of Chemistry
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Last updated: April 21, 2002
(i) determine the correct local point group symmetry based on the environment at the
metal. Determine the local point group symmetry as in pset #1 by disregarding H's on water,
etc. but considering ligand denticity and geometry.
(ii) draw a qualitatively correct & fully labeled crystal field splitting diagram indicating
the orbital occupancies corresponding to the ground configuration
(iii) for those cases where both high-spin and low-spin possibilities exist remark on
those factors (metal, ligand, etc) that lead the system to adopt e.g. the highspin versus the low-
spin form, and work through your choice
(iv) determine the total degeneracy of the ground configuration. The formula G!/(N!*
(G-N)!), where G is the number of boxes and N the number of equivalent spin ½ particles you
can place in those boxes applies. Note: degenerate energy levels may not include all
microstates that exist in K symmetry.
(v) Determine the term symbol(s) for the state(s) arising from the ground configuration
(tables of direct products will be distributed separately as needed to assist you in this) and
confirm that the overall degeneracy matches what you calculated in the previous part. (omit J
and M)
(vi) Assign the lowest energy spin-allowed electronic absorption band with reference to
the terms involved assuming the strong-field limit. (omit J and M)
(vii) If the complex contains unpaired electrons, calculate the spin-only magnetic
moment
A) [Os(CN)6 ]4-
B) [Ru(NH3 )6 ]2+
C) OsOF5
F) [Cr(OH2 )6 ]3+
H) Pd(PPh3 )4
I) [Co(CN)5 ]3-
J) [Fe(OH2 )6 ]2+
K) [Fe(bpy) 3 ]2+
L) [MnO4 ]2-
Problem set #1 50
Problem set #2 50
Exam #1 in class 100
Problem set #3 50
Problem set #4 50
Exam #2 in evening 150
Policy Statement: because this is a graded problem set it is expected that each student will do
his/her own work. Full credit will not be awarded for answers only: remember to show all your
work! Illegible, messy, or difficult-to-decipher work will not be graded. Copy over your work
prior to turning it in if necessary.
1. Draw and assign to their proper point groups the molecules depicted in figures 17.4, 17.5a,
16.3a, 16.5a, 16.5d, 18.5a, 18.5b, 18.7b, 18.7c, 18.9a, 18.9b, 18.14c, 19.4a, 19.4c, 19.6a, 19.7c,
19.9a from your textbook -- in each case draw a schematic for the flow of logic that led you to
your point group assignment. (17 points)
2. Make a table showing the effect of carrying out each of the C(2v) point group operations on a
set of atomic orbitals located at the origin of a Cartesian coordinate system. Use each of the s, p,
and d atomic orbitals (nine orbitals total!). Draw each orbital (labeled e.g. px) before and after
carrying out each operation and indicate indicate in the table with a +1 or -1 whether or not the
orbital’s phase is inverted upon carrying out the operation. (10 points)
3. Find the symmetry species (also called Mulliken Symbols or irreducible representations) for
the normal modes of water, using the C(2v) character table. Assume the water molecule to lie in
the Cartesian yz plane and match the normal mode symmetries with their pictures in figure 3.11
on page 84. (10 points)
4. As in the preceding problem but using the D(4h) character table for [PtCl4]2- and the diagram
in figure 3.14 on page 86. Assume the ion to lie in the xy plane with Pt at the origin and Pt-Cl
bonds along the x and y coordinate axes. (13 points)
Additional study problems (not graded but helpful for the exam) from page 90: 3.1, 3.2, 3.4,
3.8, 3.12, 3.21, 3.23, 3.25
Problem Set #2
Note: the same provisos concerning working this problem set independently and turning in clear
and easy-to-decipher work apply as for the previous problem set.
Problem 1
Read the discussion associated with figure 19.11 on page 448 of your textbook. The caption
asserts that the cis and trans isomers of the indicated platinum complex can be distinguished by
infrared spectroscopy. Assigned the isomers to their proper point group, and using the
associated character table, find the Mulliken symbols associated with the indicated asymmetric
and symmetric stretches for both isomers. Determine if these stretches are of the same
symmetry as the x, y, z electric dipole operators, and thereby verify the assignment given in the
text.
Carbonyl stretching bands are very useful in the characterization of transition metal carbonyls.
As an introduction to this look at the information in figure 23.2 on page 586 of your textbook. On
page 591 of your textbook consult the worked example 23.1, with its two pictures of transition-
metal carbonyl complexes. Assign the chromium carbonyl depicted to its proper point group, and
determine the number and symmetry types of the CO stretching bands that should be observed in
this molecule's infrared spectrum.
Below the chromium complex is depicted a rhodium species, and likewise for this species you
should determine the number and symmetry types of the carbon monoxide stretching bands in
the correct point group for this planar molecule. Determine not only the number of bands
expected and their symmetries, but also indicate which of these are expected to be observed in
the infrared spectrum.
On page 595 of your textbook consult compound labeled (f) in figure 23.10. Assign this molecule
to its point group, determine the number and symmetry types of the expected CO stretches for
this molecule, and indicate which of these will be infrared active according to the selection rule.
Also, for both the chromium and rhodium systems, derive pictures of each of the CO stretching
vibrations (labeled with appropriate Mulliken symbols), along with normalized expressions for the
symmetry adapted linear combinations.
Problem 2
Figure 4.14 on page 100 of your textbook develops the molecular orbital diagram for water. Our
first exercise in connection with this diagram will be to construct a table showing how all the
valence atomic orbitals of the system are permuted upon carrying out the group operations. This
problem takes advantage of the C(2v) point group, so you should consult the relevant character
table. Label the hydrogen atoms A and B respectively, and write out the group operations across
the top of the table, assuming the water molecule to lie in the yz plane. Then complete the table
showing how each of the six valence orbitals of the system are permuted upon carrying out the
group operations.
Note that since the oxygen atom resides on the intersection of all the symmetry elements, its z
axis should be taken to coincide with the molecular C(2) axis. On the other hand, it is common
when considering peripheral groups that are symmetry related to direct their local z axes toward
the central atom. This is the case for the hydrogens.
Note that your book refers to "Ligand group orbitals", whereas I will frequently use the term
"Symmetry Adapted Linear Combinations". These terms may be used interchangeably.
Problem 3
You should recognize that the molecular orbital diagrams can be simplified considerably through
the application of symmetry concepts. For example, it can be considered that there is for each
molecular system a separate molecular orbital diagram for each of the symmetry species, i.e. for
each of the Mulliken labels. For this reason, you can divide your analysis of the molecular
orbitals of the system up into parts according to the number of symmetry species spanned.
Write down the configuration for the ground state of water in terms of the four symmetry species
of the C(2v) point group, including both occupied and virtual orbitals. Identify each of the MOs as
bonding, nonbonding, or antibonding. Sketch clearly each of the molecular orbitals.
Problem 4
On page 256 of your textbook is depicted an alane solvate. Substitute water in place of the THF
molecules and derive the MO diagram for this system in the appropriate point group. Present the
MO diagram not as a whole but rather as separate MO diagrams for each symmetry species
encompassed. Sketch clearly and label each of the MOs.
Problem 5
Pentaborane-9 (rocket fuel) is depicted in the center of figure 12.18 of your text on page 272.
Label all the atoms and identify the symmetry-related sets. For each of the symmetry-related
sets, find the corresponding symmetry-adapted linear combinations (SALCs) of atomic orbitals.
Sketch clearly all of the SALCs and write down normalized expressions for them. Write down the
most probable configuration for the ground state of pentaborane-9 in terms of the configurations
for each of the represented symmetry species.
Problem 6
Assume R = H for compound 12.22 (page 268 of your text). Assign the system to a point group,
identify symmetry-related sets of valence atomic orbitals, and derive and sketch clearly all the
corresponding SALCs. Then write down a probable configuration for the system’s ground state in
terms of the represented symmetry species.
Problem 7
As in the preceding problem but for N2O4 (see Figure 14.11 on page 335 of your text).
1.
On page 450 of your textbook is given a list of terms introduced in the chapter. Give, in your own
words, a complete yet succinct definition for each one of these terms.
2.
Using the methods and concepts introduced in the Monday March 4 lecture, derive the splitting
diagrams pictured in figure 20.10 of your textbook, on page 460. Do your derivations differ in any
substantial respect with the results pictured in the text? If so, comment on the likely origin of any
discrepancies.
3.
A list of terms is provided on page 485 of your textbook. Provided a succinct yet complete
definition of each of these terms, using your own words.
4.
On page 486 of your textbook you will find problems 20.2, 20.3, 20.5, 20.8, 20.12, 20.15, 20.18.
Solve them.
5.
Consider the Crystal field splitting diagrams for a nickel(II) complex in D(4h) symmetry, with
sigma-only donor ligands. Now, recollecting the MO picture in box 20.4 on page 464 of your
textbook, consider a nickel(II) complex with a single carbon monoxide ligand included in a
square-planar arrangement of ligands. Consider this in C(2v) symmetry, showing which d orbital
(s) goes to lower energy vis-a-vis the D(4h) parent complex.
Be sure to label all orbitals in both diagrams with the appropriate symmetry label (Mulliken label).
6.
Find the oxidation state, number of d electrons, and group in the periodic table for the metal in
each molecule depicted in figures 19.3, 19.5, 19.6, 19.7, 19.8, 19.9, 19.12, and also in problem
19.11.
7.
Explain in your own words what the relationship is between the figure of figure 20.12 and the
corresponding Crystal field view of the same situation.
8.
On page 476 of your textbook you will find self-study exercises 1, 2, and 3. Give corresponding
Crystal field splitting diagrams, fully labeled with symmetry labels, and populated with the correct
number of electrons in each case.
1
(e) Ni(η5-C 5 H5 )2 can "distort" to a more stable "18 electron" structure that contains another type
of η x-C 5 H5 ligand bound to nickel. Draw this structure and rationalize why it is an 18e species.
(f) Although η 5-C 5H5 compounds are known for main group elements (see chapter 18), η5-C 5 H5
bonding in p-block elements (e.g., in [Pb(η 5-C 5H5 )2 ]n is usually relatively weak. Explain in
orbital terms why η5-C 5H5 bonding might be weak in the p-block elements versus the transition
metals.
(g) Compounds that contain a η 5-C 5Me5 ligand are usually much more robust than analogs that
contain a η 5-C 5H5 ligand. Provide two or more reasons why that might be the case. (Note that
the pKa of pentamethylcyclopentadiene is significantly higher than that of cyclopentadiene as a
consequence of the greater electron-donating ability of C versus H.)
(h) Would you expect Fe(η 5-C 5Me5 )2 to be a stronger or a weaker reducing agent than Fe(η5-
C5H5) 2 and why?
Ho Hi Hi Ho
Rh
Ho Hi Hi Ho
temperatures only one singlet of area eight is observed for these protons. Explain what is
happening at high temperatures that leads to "equilibration" of the Hi and Ho protons.
(Dissociation of ethylene can be excluded by other experiments.)
3
(e) η3-C 3H5 ligands do not rotate without a barrier about the axis shown in the platinum complex
shown below. Explain why not in orbital terms.
+
PEt3
Pt
PEt3
(f) Three allyl resonances in the ratio of 2:2:1 are observed in the proton NMR spectrum of the
platinum complex shown above. Explain why. When the NMR sample (in acetone-d6) is heated
the resonances of area two coalesce to give two patterns in the ratio of 5:1. Explain.
1
1. (12 points total) Consider two parallel, eclipsed cyclobutadiene rings that ultimately will
receive an iron atom between them to form currently unknown biscyclobutadiene iron (D4h
symmetry).
(a) (5 pts) Construct the molecular orbitals for the two rings in this eclipsed orientation from the
Hückel MO's on each cyclobutadiene and label them in the D4h point group.
(b) (5 pts) Look up the symmetries of the s, p, and d orbitals in the D4h point group and construct
and discuss an MO scheme that describes the bonding in hypothetical biscyclobutadiene iron.
(c) (2 pts) Would you expect hypothetical biscyclobutadiene iron to be a stable species at 22°C?
Why or why not?
2. (15 points total) Dicobalt octacarbonyl can take the two forms (A and B), which have C2v
and D3d symmetries, respectively, assuming that the Co-C-O bond angles are 180°.
O OC CO
OC
OC C CO
OC Co Co CO OC Co Co CO
OC C CO OC CO
O OC
A B
A1g 1 1 1 1 1 1 z2
A2g 1 1 -1 1 1 -1 Rz
A1u 1 1 1 -1 -1 -1
A2u 1 1 -1 -1 -1 1 z
Eu 2 -1 0 -2 1 0 (x,y)
2
(a) (5 pts) Assume that the CO stretches can be isolated from the rest of the atomic
displacements in the molecule. Using an arrow between each C and O as an indicator of a CO
stretch, write down the representation for the eight CO stretches (arrows) in molecule B, reduce
it to a sum of irreducible representations, and state on that basis how many CO stretches could in
theory be observed in the IR spectrum of B.
(b) (3 pts) Bridging CO stretches are observed at lower energies than terminal CO stretches.
(Why?) Therefore the bridging CO stretches in molecule A can be analyzed separately. You can
see by inspection that two IR active bridging CO stretches would be observed in A.
Nevertheless, write a representation for the two bridging CO stretches in A, reduce it, and prove
that they are both IR active.
(c) (5 pts) Go through the same exercise to analyze the six terminal CO stretches in molecule A.
(d) (2 pts) Assume that Co2 (CO)8 has either one form or the other, and that four CO stretches
are observed experimentally in the region between 1700 and 2000 cm-1. On this basis which
structure must Co2 (CO)8 have?
+ +
Fe Fe
F3P CO Me3P CO
F3P Me3P
A B
(d) In (CO)5Cr=C(C 6H5)(NMe2), a "Fischer Carbene" complex, the methyl groups on the
nitrogen atom are inequivalent on the NMR time scale at low temperature in the proton NMR
spectrum. Explain why this is the case.
(e) What is at least one unambiguous piece of evidence that the Ta=C bond in compounds such
as (η5-C 5H5)2Ta(CH2)(CH3) or (Me3CCH2)3 Ta=CHCMe3 is polarized (+) on Ta and (-) on
the α carbon of the alkylidene ligand?
3
4. (16 points total) "Bent" biscyclopentadienyl complexes are found for metals in groups 4, 5, or
6. Only three frontier orbitals are available for forming three bonds to ligands. The orbitals are
shown below. (Orbital A can also be empty or can contain a lone pair; A is a dz2-like orbital.)
Note that all three orbitals lie in the plane that passes between the two cyclopentadienyl ligands
(i.e., in the plane of the paper). Show how these orbitals are used in the following circumstances
and describe and draw the structure of each species unambiguously. (If necessary, draw views
from the "side" or "front" (with the Cp's going into the page), as well as from the "top", as shown
below.)
+ +
Cp -
- Cp Cp
Cp Cp Cp
-
+
A B C
(f) (3 pts ) Imido ligands, such as the one shown in the Zr compound shown in (e) normally bind
to a metal to give a "pseudo triple bond." Why is that not possible in this circumstance, and
where are the electrons located? Can you tell if the imido ligand is bent or linear on this basis
(g) (3 pts ) The ethylene ligand in the niobium compound shown in (d) shows no signs of
rotating about the Nb-ethylene bond on the NMR time scale. Such a rotation is not possible for
1. (30 pts total; 5 each) Explain the mechanism of each of the following reactions using
appropriate and clear formulas and structures of plausible intermediates.
Br
Pd(PPh3)4 cat
(a) OMe + C6H 5MgBr OMe
toluene
(d) The metathesis of cis-2-pentene in toluene to give a mixture of cis and trans 2-pentene
(50%), 3-hexene(25%), and 2-butene (25%) initiated by Mo(CHCMe3)(N-2,6-
Me2C6H3)[OCMe(CF3)2]2.
(e) Formation of acetic acid from methanol and CO catalyzed by [Rh(CO)2I2]- and HI; overall
CH3OH + CO → CH3OH.
(f) Hydrogenation of terminal olefins by Rh(PPh3)3Cl at 25°C and 1 atm of H2 in (for example)
benzene.
D2 H
HD
D
NBD
What does this result tell you about the mechanism of this hydrogenation reaction, in contrast to
the mechanism of hydrogenation of terminal olefins by Rh(PPh3)3Cl?
(c) (3 pts) When chloride is added to the reaction in (b) before norbornadiene is consumed, the
hydrogenation of norbornadiene ceases, and it can be shown that Rh(NBD)(PPh3)Cl is present,
even when NBD and dihydrogen are still present. Explain how and why chloride "hijacks" the
metal and terminates the catalytic reaction.
(d) (4 pts) Instead of "oxidative addition" of benzyl chloride to the cobalt complex shown
below, the benzyl chloride bond is split homolytically to yield two new Co(III) species. Explain
how this reaction occurs and why it takes this pathway.
(e) (7 pts) When the dilithium salt of the "linked" cyclopentadienyl system shown below is
added to ZrCl4, meso and racemic "ansa" zirconocene dichloride complexes are formed.
(i) Explain what these species are and why they do not interconvert readily. (ii) Both types can
be alkylated to give analogous dimethyl species. Explain why the racemic dimethyl species,
upon activation by Ph3C+B(C6F5)4- in chlorobenzene, leads to a catalyst for the formation of
isotactic polypropylene that is more efficient than [(η5-C5H5)2Zr(CH3)]+[B(C6F5)4]-.
Li+ -
- Li+
1
1. (30 pts total; 5 each) Explain the mechanism of each of the following reactions using
appropriate and clear formulas and structures of plausible intermediates. (You may leave off the
permanent ligands when drawing intermediates.)
(a) The Ring Opening Metathesis Polymerization (ROMP) of norbornene to give polynorbornene
by an alkylidene catalyst such as Mo(CHCMe3)(N-2,6-Me2C6H3)[OCMe3]2.
(b) The asymmetric "Ring-Opening/Cross Metathesis" reaction shown below: (You do not have
to explain how the enantiomer shown arises, just the basic mechanism.)
t-Bu i-Pr
i-Pr
O N
Mo
O Ph
+ Ph
Ph
(c) The "Desymmetrization" reaction shown below: (You do not have to explain how the
enantiomer shown arises, just the basic mechanism.)
Me Me
N
Me
O Mo Ph
O Me
1 mo l % c atalys t Me
O - C 2H 4 H
Me Me Me
O
no solvent,
22 °C , 5 m in
93% ee, 85% y ield
2
(d) The catalytic oxidation of a hydrocarbon (RH) by the Fe(III) porphyrin species shown below
(a cytochrome monooxygenase).
S(Cys)
(porph)N N(porph)
Fe
(porph)N N(porph)
RH + 2 H + + 2e + O2 H 2O + ROH
(e) The catalytic reduction of dinitrogen to ammonia at a Mo(III) center using 6 protons and 6
electrons (a "Chatt-type" dinitrogen reduction).
(f) Explain how Vitamin B12, a coenzyme, helps catalyze the rearrangement reaction shown
below. (MeCH(NH2)OH subsequently loses ammonia to yield acetaldehyde.)
CH 2CH2OH CH3CHOH
NH 2 NH 2
2. (20 points total; 2 points each) Solid state chemistry. Explain the following:
(a) The difference between cubic close packed and hexagonal close packed.
(b) The difference between body-centered cubic face-centered cubic.
(c) What is meant by polymorphism and give an example.
(d) Interstitial alloy (including an example).
(e) A metallic conductor.
(f) An insulator.
(g) A semiconductor.
(h) A graphite intercalation compound.
(i) Show from the zinc blend unit cell that the empirical formula of a compound with that
structure (e.g., ZnS) is MX.
(j) Show from the unit cell of perovskite that the empirical formula is CaTiO3.
5.03 Exam-2*
03/20/02, 7:30-9:00pm
Room # 2-190
* Evening exam
General Instructions: This is a closed book and closed notes exam. Please
answer all questions in the blue books provided. Illegible work will not be graded.
Please read through the entire paper (total 4 pages) before beginning to answer the
problems. You have 90 minutes for this exam; therefore, it is advisable to maximize
your points by first attempting those questions that are relatively easy and/or carry
more points. Good Luck!
1
1. Coordination Chemistry – general (20pt)
1.1. What dn configuration is found most commonly for a square planar platinum
complex? (2pt)
1.2. What dn configuration is found most commonly for an octahedral metal complex
of cobalt? (2pt)
1.3. Define the term “linkage isomerism” with the help of an example. (4pt)
1.4. Draw the three coordination polyhedra that are typical of coordination number
seven. (9pt)
1.5. Werner’s proof of the coordination theory relied most heavily on what physical
property of octahedral metal complexes? (3pt)
2.1. For an octahedral metal complex, which of the metal d orbitals are involved in
sigma bonding to the ligands? (2pt)
2.2. Calculate the CFSE for [Cr(OH2)6]3+ and illustrate schematically how you
calculated this quantity. (8pt)
2.3. From a physical point of view based on the CF model, explain why there is a
stabilization associated with the chromium(III) ion in an octahedral field. (4pt)
2.4. Why is it rare to encounter a low-spin tetrahedral coordination complex? (6pt)
2.5. If you were to attempt to synthesize a low-spin tetrahedral complex, which ligand
would you choose: chloride or cyanide? Explain your choice. (4pt)
2.6. Which of the following is expected to be subject to a substantial Jahn-Teller
distortion: [Cr(OH2)6]2+ or [Fe(OH2)6]2+? Explain your choice. (8pt)
1.1. Neglecting the effects of charge and assuming sigma effects to be the same,
which of the following is expected to have the largest value of ∆o: Mo(CO)6,
Mo(NMe2)6, or [Mo(NH3)6]3+? Very briefly explain your choice. (4pt)
1.2. Which the smallest? Very briefly explain your choice. (4pt)
1.3. Indicate for which of the three the energy of the T2g set is at a maximum, and
draw a schematic MO diagram illustrating why. (9pt)
4.1. What is the total degeneracy (number of microstates) for a d1 ion (e.g. Ti3+) in
spherical symmetry? (3pt)
4.2. In octahedral symmetry? (3pt)
4.3. What is the ground term for a d1 ion in tetrahedral symmetry? (4pt)
4.4. What is the spin multiplicity in the latter (tetrahedral) case? (2pt)
4.5. What is the ground term for [PtCl4]2-? (5pt)
4.6. Electronic transitions for [PtCl4]2- will be spin-allowed if the excited states have
what spin multiplicity? (2pt)
2
4.7. The characteristic, intense color of [Ru(bpy)3]2+ is due to (a) d-d bands, (b)
MLCT bands. Indicate which, and explain. (6pt)
4.8. An Orgel diagram can be referred to also as a correlation diagram. What are the
quantities correlated in an Orgel diagram and as a function of what are they
correlated? (3pt)
1.1. What is the spin-only value of µeff expected for [Cr(NH3)6]Br2 if the complex is
high-spin? (3pt)
1.2. If it is low-spin? (3pt)
1.3. The complex [Co(OH2)6]2+ exhibits a µeff greater than that predicted by the spin-
only formula. Explain the origin of this effect. (5pt)
1.4. A Curie paramagnet exhibits a linear relationship between the temperature and
what quantity? (2pt)
1.5. Liquid oxygen (which incidentally is blue) is (a) attracted into (b) repelled away
from a magnetic field. Explain your choice. (3pt)
1.6. The spin multiplicity of the ground term for dioxygen is what? (2pt)
3
Relevant Data:
H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Character tables:
linear
2C4 2 2 quadratic cubic
D4h E C2 2C'2 2C''2 I 2S4 h functions,
(z) v d functions functions
rotations
A1g +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 - x2+y2, z2 -
A2g +1 +1 +1 -1 -1 +1 +1 +1 -1 -1 Rz - -
B1g +1 -1 +1 +1 -1 +1 -1 +1 +1 -1 - x2-y2 -
B2g +1 -1 +1 -1 +1 +1 -1 +1 -1 +1 - xy -
Eg +2 0 -2 0 0 +2 0 -2 0 0 (Rx, Ry) (xz, yz) -
A1u +1 +1 +1 +1 +1 -1 -1 -1 -1 -1 - - -
A2u +1 +1 +1 -1 -1 -1 -1 -1 +1 +1 z - z3, z(x2+y2)
B1u +1 -1 +1 +1 -1 -1 +1 -1 -1 +1 - - xyz
B2u +1 -1 +1 -1 +1 -1 +1 -1 +1 -1 - - z(x2-y2)
(xz2, yz2) (xy2,
Eu +2 0 -2 0 0 -2 0 +2 0 0 (x, y) -
x2y), (x3, y3)
4
5.03 Syllabus and Lecture Plan - First Half of Spring, 2002