Inorganic Chemistry (MIT Lecture Notes)

5.03 Syllabus and Lecture Notes

Syllabus and Lecture Notes The syllabus is available here (updated!). The point distribution for the first half of the semester is here. 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. Lecture

Date

Topic

Lecturer

1

2/6/02

Symmetry Elements and Operations

CCC

Notes

Readings

PDF 3.1-3.2 WRL*

2

2/8/02

Point Group Assignments

CCC

PDF

3.3-3.4

3

2/11/02

Character Tables

CCC

PDF

3.5-3.6, Appendix 3

4

2/13/02

IR Spectroscopy and Symmetry

CCC

PDF

3.7-3.8

5

2/15/02

LGO's and MO's

CCC

PDF

4.1-4.4

6

02/19/02

Simple MO's

CCC

PDF

4.5-4.7

7

02/20/02

Boron Hydride Bonding

CCC

PDF

12.1-12.5, 12.11

8

02/22/02

N and P oxides

CCC

PDF

14.8-14.11

9

02/25/02

Group 16 bonding

CCC

PDF

15.1-15.4, 15.7-15.8, 15.10

10

02/27/02

Intro to Coordination Chemistry

CCC

PDF

Ch. 19

11

03/01/02

Exam #1

CCC

12

03/04/02

Crystal Field Theory

CCC

PDF

20.1-20.3

13

03/06/02

Pi-donor/acceptor MO's

CCC

PDF

20.4

14

03/08/02

Electronic Spectra

CCC

PDF

20.5-20.6

15

03/11/02

Orgel and Tanabe-Sugano diagrams

CCC

PDF

20.6

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Lectures 1-9 and Readings

5.03 Syllabus and Lecture Notes

03/13/02

Magnetic Properties of Coord. compds.

CCC

PDF

20.8

03/15/02

Ligand Subsitution: Square Planar Complexes

CCC

PDF

25.1-25.3

18

03/18/02

Ligand Substitution: Octahedral Complexes

CCC

PDF

25.4

19

03/20/02 Electron Transfer

CCC

PDF

25.5

20

03/22/02

CANCELLED

CCC

21

04/01/02

Alkyls of Groups 1, 2, 12, 13, and 14

RRS

PDF

18.1-18.5

22

04/03/02

Transition metal alkyls and hydrides

RRS

PDF

23.2-23.3, 23.7, 23.9

23

04/05/02

ηx-ligands

RRS

PDF

23.10-23.11

24

04/08/02

ηx-ligands and fluxional processes

RRS

25

04/10/02

Metal carbonyls and clusters

RRS

PDF

23.4

26

04/12/02

Multiple metal-ligand and metal-metal bonds

RRS

PDF

23.12

27

04/17/02

Reactions at a transition metal center

RRS

PDF

23.7 (repeat)

28

04/19/02

Homogeneous catalysis

RRS

PDF

26.1-26.3

29

04/22/02

Homogeneous catalysis

RRS

PDF

26.1-26.3

30

04/24/02 Exam #3 in class

RRS

31

04/26/02

Catalysis

RRS

PDF

26.4-26.6

32

04/29/02

Catalysis

RRS

PDF

26.4-26.6

33

05/01/02

Metals in Biology

RRS

PDF

28.1-28.5

16

17

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PDF Ferrocene 23.13-23.15 MO's

5.03 Syllabus and Lecture Notes

34

05/03/02

Metals in Biology

RRS

PDF

28.1-28.5

35

05/06/02

Metals in Biology

RRS

PDF

28.1-28.5

36

05/08/02

Solid State Chemistry

RRS

PDF

5.1-5.11, 5.17

37

05/10/02

Solid State Chemistry

RRS

PDF

27.1-27.4, 27.6

38

05/13/02

Lanthanides and Actinides

RRS

PDF

Chapter 24

39

05/15/02

Nuclear Chemistry

RRS

PDF

Chapter 2

Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: May 7, 2002

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5.03 Course Home Page

Spring 2002 MWF10 2-105 Prof. Christopher C. Cummins Prof. Richard R. Schrock

Presents principles of chemical bonding and molecular structure, and their application to the chemistry of representative elements of the periodic system.

--Welcome to 5.03. Check the Announcements page for page update information.

Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: February 13, 2002 Initial concept by Tet Matsuguchi

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5.03 Announcements

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 http://web.mit.edu/5.03/www/announcements.html (1 of 3) [2002-05-14 20:25:15]

5.03 Announcements

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

03/05/02: Problem Set #3 is up! -Adam 02/26/02: I forgot to announce it, but the solutions to pset #2 have been posted since this afternoon. -Adam 02/26/02: Adam's EXTRA office hours/review session will be W 2-4 in 8-119. Amrit's extra office hours/review session will be R 4-?, also in 8-119. -Adam 02/26/02: The 3-D molecule files Amrit and I showed in recitation are online in the notes section. You will have to download a VRML viewer, and a link to the one I use is included. -Adam 02/26/02: Adam will hold extra office hours W 2-4, location TBA, so check back! Amrit will hold extra office hours R 4-?, location TBA. -Adam 02/19/02: Amrit and Adam's office hours are moved to room 2-131. Come and see what all the fuss is about Thursday at 5. Also, the P.S. 1 key is posted -Adam 02/17/02: P.S. 2 is up -Adam 02/13/02: Lecture Notes 1-4 are up! 02/12/02: Notes from Lectures 1-3 will be up asap. The links to the notes go to blank spots at the momment, though. -Adam 02/12/02: Recitation#5 is permantly moved to room 2-135. -Adam 02/09/02: Recitation#5 on tuesday at 10 am will take place in 2-135 instead of 8-205 for this week only. 02/06/02: The syllabus page should be updated with the

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5.03 Announcements

correct lecture topics up to P.S. 1's due date. All PS due dates are correct through exam #2 on the calender page (as far as I know! email me at [email protected] if anything is wrong!) -Adam 02/05/02:

Recitation will begin Monday (02/11/02) -Adam

Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: May 7, 2002

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5.03 Information

Spring Term 2002

5.03 Inorganic Chemistry I This subject deals primarily with chemical bonding and molecular structure, and their application to the chemistry of representative elements of the periodic system. There will be three lectures per week and one recitation section devoted to discussion of the assigned problems and lecture material. Lectures: MWF, 10:05AM-10:55AM, Room 2-105 Instructors Teaching Assistants Administration: Kris Grabarek, Assistant Director of Chem. Education, Room 2-204, x3-0909, [email protected] Laura Howe, Web Manager, Room 2-204, x8-7492, [email protected] Jennifer Picray, Course Manager, Room 2-204, x3-7271, [email protected] 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).

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5.03 Information

Grading: There will be a total of 1000 points for the semester. The distribution for the first half may be found here.

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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5.03 Information

Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: February 6, 2002

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5.03 Faculty and Staff

Instructors: Prof. [email protected] Christopher 2-227 x3-5332 Office Hours: 3-4 C. TW in 2-227 Cummins Prof. Richard R. Schrock

6-331 x3-1596 [email protected]

Teaching Assistants:

Office Hours:

Adam Hock

[email protected]

R 5-6

2-131

Amritanshu Sinha

[email protected]

R 5-6

2-131

Recitations: Rec # Time Room

TA

1

W9

2-139 Adam

2

R2

2-132 Amrit

3

R1

1-134 Adam

4

T1

1-134 Amrit

5

T10

2-135 Adam

6

M1

2-136 Amrit

Administration: Kris Grabarek, Assistant Director of Chem. Education, Room 2-204, x3-0909, [email protected] Laura Howe, Web Manager, Room 2-204, x8-7492, [email protected] Jennifer Picray, Course Manager, Room 2-204, x3-7271, [email protected]

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5.03 Faculty and Staff

Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: February 19, 2002

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5.03 Course Calendar

Course Calendar February, 2002 Monday

Tuesday

Wednesday

Thursday

Friday 1

4 Registration Day

5

6 Lecture 1 Symmetry Elements and Operations

11 Lecture 3 Character Tables

12

13 14 Lecture 4 IR Spectroscopy and Symmetry

15 Lecture 5 LGO's and MO's

20 21 Lecture 7 Boron Hydride BondingPDF

22 Lecture 8 N and P oxides PDF

18 President's 19 Day Lecture 6 Simple MO's PDF Monday Schedule 25 Lecture 9 Group 16 bondingPDF

26

Problem Set #2 Due in class

7

8 Lecture 2 Point Group Assignments

Problem Set #1 Due in class

27 28 Lecture 10 Intro to Coordination Chemistry PDF

March, 2002 Monday

Tuesday

Wednesday

Thursday

Friday 1 Lecture 11 Exam #1 in class Room TBA

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5.03 Course Calendar

4 Lecture 12 Crystal Field Theory PDF

5

11 12 Lecture 15 Orgel and Tanabe-Sugano diagrams PDF Problem Set #3 Due in class 18 19 Lecture Ligand Substitution: Octahedral Complexes PDF Problem Set #4 Due in class 25 Spring Break Week

26

6 7 Lecture 13 Pi-donor/acceptor MO's PDF

8 Lecture 14 Electronic Spectra PDF Add Date

13 Lecture 16 Magnetic Properties of Coord. compds. PDF

15 Lecture 17 Ligand Subsitution: Square Planar Complexes PDF

14

20 21 Lecture 19 Electron Transfer PDF Exam #2 Evening Exam 7:30 PM in 2-190 27

28

22 Lecture 20 Cancelled due to the exam 3/20.

29

April, 2002 Monday

Tuesday

Wednesday

Thursday

1 2 Lecture 21 Alkyls of Groups 1, 2, 12, 13, and 14 PDF

3 Lecture 22 Transition metal alkyls and hydrides PDF

4

5 Lecture 23 ηx-ligands PDF

8 Lecture 24 ηx-ligands and fluxional processes PDF

10 Lecture 25 Metal carbonyls and clusters PDF

11

12 Lecture 26 Multiple metal-ligand and metal-metal bonds PDF

9

Problem Set #5 Due in class

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Friday

5.03 Course Calendar

15 Patriot's Day Holiday

16 Patriot's Day Holiday

22 23 Lecture 29 Homogeneous catalysis PDF

17 Lecture 27 Reactions at a transition metal center PDF

18

19 Lecture 28 Homogeneous catalysis PDF

24 Lecture 30

25 Drop Date

26 Lecture 31 Catalysis PDF

Exam #3 in class

Problem Set #6 Due in class 29 30 Lecture 32 Catalysis PDF

May, 2002 Monday

Tuesday

Wednesday 1 Lecture 33 Metals in Biology PDF

Thursday 2

Friday 3 Lecture 34 Metals in Biology PDF Problem Set #7 Due in class

6 Lecture 35 Metals in Biology PDF

7

8 Lecture 36 Solid State Chemistry PDF

9

10 Lecture 37 Solid State Chemistry Problem Set #8 Due in class

13 Lecture 38 Lanthanides and Actinides

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14

15 Lecture 39 Nuclear Chemistry

16

17

5.03 Course Calendar

20

21

22

23 Final Exam

24

9:00 AM in 2-190 27

28

29

30

31

Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: May 1, 2002

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5.03 Assignments

Problem sets are due in class on the due date. Problem Set

Due

Solutions

1

PDF

02/15/02

PDF

2

PDF

02/25/02

PDF

3

PDF

03/11/02

PDF PDF

4

PDF*

03/18/02

fixed pg 3

5

PDF

04/10/02

PDF

6

PDF

04/22/02

PDF

7

PDF

05/03/02

8

PDF

05/10/02

*

updated!!

Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: May 6, 2002

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5.03 Exams

All Examinations will be closed-book and closed notes. Exam

Date

Room

Info

Solutions

Exam I

03/01/02

TBA

PDF

PDF

Exam II*

03/20/02

2-190

PDF

PDF

Exam III

TBA

TBA

Exam IV

TBA

TBA

Final

TBA

TBA

*Exam II is at 7:30 pm!

Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: April 4, 2002

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5.03 Resources

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. Club Chem - Are you Course 5? Interested in Chemistry? Join ClubChem! Faculty Dinners, Chemistry Magic Shows, etc. MIT Chemistry Department WebElements Periodic Table - The first periodic table on the WWW. It also has a large amount of information about each individual element such as its history, pictures, compounds, uses, etc. Character Table (at the bottom!)- Handy if you are ever caught without a copy of a chemist's best friend! This is a math site, and presents the theory that culminates in character tables. Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources

Department of Chemistry Send comments and suggestions to course webmaster: [email protected] Last updated: April 21, 2002

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Analyze the each of the following complexes as follows: (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 lowspin 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 ]4B) [Ru(NH3 )6 ]2+ C) OsOF5 D) [mer-Re(PMe3 )3 Cl3 ]2+ E) [TcO 2 (en)2 ]+ (mutually trans oxo ligands) F) [Cr(OH2 )6 ]3+ G) [Cu(NH3 )(OH2 )5 ]2+ H) Pd(PPh3 )4

I) [Co(CN)5 ]3J) [Fe(OH2 )6 ]2+ K) [Fe(bpy) 3 ]2+ L) [MnO4 ]2M) [Mn(H2 O)6 ]2+

Grading Scheme for 5.03, Spring 2002, first half of the Semester

Problem set #1 Problem set #2 Exam #1 in class Problem set #3 Problem set #4 Exam #2 in evening Total points: 450

50 50 100 50 50 150

5.03 Problem Set #1, Spring 2002, Due in class on Friday, February 15 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 transitionmetal 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

5.03 Problem Set #5 Due 4/10/02 1. (15 points total; 2.5 points each) (a) Textbook problem 18.6a. (b) Textbook problem 18.6b. (c) The reactivity of LiR compounds in a given solvent such as diethyl ether follows the order R = Me < n-butyl < t-butyl. Explain the increase in reactivity in terms of the structures of LiR Compounds that are likely to be

O

O

O

O

present in each case. (Look at and think about Table 18.1.) (d) Addition of a "crown ether" such as benzo-12-crown-4 to a lithium reagent in solution often leads to a dramatic increase in reactivity that can be traced to a much more nucleophilic alkyl carbon atom. Explain why this is the case.

benzo-12-crown-4

(e) Explain why W(CH2 CH3 )6 is unlikely to be prepared by treating WCl6 with six equivalents of ethyllithium in pentane. (f) Explain why ethylation of a transition metal species is sometimes the way to prepare a metal hydride complex. Where would one expect to observe a transition metal hydride resonance in a proton NMR spectrum? e1 u*

2. (20 pts; 2.5 each) Metallocenes and related species are ubiquitous in organotransition metal chemistry. A qualitative molecular orbital diagram for a metallocene is shown to the right. Note that the ordering of the levels within the dashed box is not correct for all metallocenes, on the basis of certain facts such as the number of unpaired electrons. (The ordering of the higher levels is also uncertain, but less consequential in most circumstances.) Explain the following and show the

a2 u* e2 g* a1 g* e2 u e 1 g* a1 g e2 g

occupancy of the MO's in the diagram for parts (a) - (d):

e1 u

(a) V(η5-C 5H5) 2 is a violet paramagnetic solid.

e1 g

(b) Cr(η5-C 5 H5 )2 has two unpaired electrons. (c) Ni(η5-C 5 H5 )2 has two unpaired electrons.

a2 u

(d) Co(η5-C 5H5) 2 can be oxidized readily to {Co(η5-C 5 H5 )2}+.

a1 g

2 (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(η5C5H5) 2 and why? 3. (15 pts total; 2.5 each) (a) In the 100 MHz proton NMR spectrum of Fe(η 5-C 5H5 )(η1-C 5 H5 )(CO)2 at 80°C the resonances for the η 5-C 5H5 and the η 1-C 5H5 ligands are both sharp singlets of area 5. Explain why the resonance for the η 1-C 5H5 ligand is a sharp singlet. (b) Explain in terms of bonding to the metal why a η5-C 5R5 ring (R = H or Me) always "rotates" rapidly about the centroid-metal axis. (c) At -100 °C three resonances for the five protons in the η1-C 5H5 ligand in (a) are found in a ratio of 2:2:1. Explain why this is the case. (d) Rh(η5-C 5H5)(η2-C 2H4)2 has a pseudo trigonal structure (see drawing below) with the ethylene ligands oriented perpendicular to the pseudo trigonal plane. At low temperatures two complex resonances are observed for the Hi and Ho protons, each with area 4.

Ho

Hi

Hi

Ho

Hi

Ho

At high

Rh Ho

Hi

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.

+ Pt

PEt3 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

5.03 Problem Set #6 Due 4/22/02 53 points total 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 C

OC OC

Co

Co

CO

C

OC

OC

CO OC

CO

OC CO

Co OC

O

Co CO

OC

A

CO

B

D3d

E

2C3

3C2

i

2S 6

3σd

A1g

1

1

1

1

1

1

A2g

1

1

-1

1

1

-1

Eg

2

-1

0

2

-1

0

A1u

1

1

1

-1

-1

-1

A2u

1

1

-1

-1

-1

1

Eu

2

-1

0

-2

1

0

z2 Rz (Rx , Ry )

z (x,y)

(x2 - y2 , xy), (xz, yz)

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? 3. (10 pts total; 2 each) (a) When CO coordinates (weakly) to BH 3 its stretching frequency actually increases. Explain why. (Note that BH 3 is purely a Lewis acid.) (b) Predict whether the highest energy IR absorption in [Mn(CO)6] + will be higher or lower in energy than the same absorption in Mo(CO)6, and explain why. (c) Predict whether ν CO will be higher or lower in energy in compound A vs. compound B and explain why. + F3P F3P

Fe CO A

+ Me3P Me3P

Fe CO 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

(a) (2 pts ) Cp2 TaH3 . (b) (2 pts ) Cp2 WCl2 . (c) (2 pts ) Cp2 Ta(CH2 )(CH3 ) (d) (2 pts ) Cp2 Nb(η2-CH2CH2 )(C 2 H5 ) (e) (2 pts ) Cp2 Zr(N-t-Bu)(THF) (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 alone? Why or why not? (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 orbital reasons in this circumstance. Why not?

1

5.03 Problem Set #7 Due 5/3/02 50 points total 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

(b) Hydroformylation of propylene by RhH(CO)(PPh3)3 in neat PPh3 at 100°C. (c) The polymerization of ethylene by [(η5-C5H5)2Zr(CH3)]+X- where X- is a "weakly coordinating" anion such as [B(C6F5)4]-. (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-2,6Me2C6H3)[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. 2. (20 points total) Explain the following: (a) (3 pts) Ir(CO)(PPh3)2Cl is known to add dihydrogen reversibly to yield IrH2(CO)(PPh3)2Cl, yet Ir(CO)(PPh3)2Cl is not a hydrogenation catalyst for any olefins at 25°C and 1 atm of H2 in (for example) benzene. Explain why IrH2(CO)(PPh3)2Cl does not react readily with olefins, while RhH2(PPh3)3Cl does. (b) (3 pts) [Rh(NBD)(PPh3)2]+ BF4- will hydrogenate norbornadiene (NBD) catalytically to norbornene in acetone. If only one equivalent of dideuterium (per NBD) is allowed to be absorbed the resulting norbornene contains deuterium in the endo positions of norbornene, i.e.

2

H

D2

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. [Co(CN)5]3- + C6H5CH2Cl -------------> [Co(CN)5(CH2Ph)]3- + [Co(CN)5Cl]3-

(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

5.03 Problem Set #8 Due 5/10/02 50 points total 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

N

O Mo O O-t-Bu

t-Bu

Ph catalyst

O-t-Bu +

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 Mo

O

O

Ph Me

1 mo l % c atalys t O Me

- C 2H 4 Me

Me H 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 NH 2

CH3CHOH 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!

Relevant data are provided on the last two pages.

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. Crystal Field Theory (32pt) 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) 3. MO Theory of Complexes with Inclusion of Pi Bonding (17pt) 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. Term Symbols, Orgel Diagrams (28pt) 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) 5. Magnetic Properties (18pt) 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 spinonly 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) 6. Ligand Substitution (25pt) 6.1. Retention of stereochemistry for substitution at square-planar platinum is indicative of an (a) associative or (b) a dissociative pathway? Explain your choice. (8pt) 6.2. Chloride opposite chloride is substituted more readily than chloride opposite ammonia, in a square planar complex. What is the name of this effect and what is its origin in MO terms? (6pt) 6.3. Rates of ligand substitution in octahedral cobalt and chromium systems typically are invariant with respect to the nature of the entering ligand, and rather seem to depend mainly on the nature of the leaving group. Of the following mechanistic alternatives, which are most consistent with the latter observation: D, Id, Ia, A? Explain your choice(s). (5pt) 6.4. In the rate law for the reaction ML5X + Y à ML5Y + X, what is the order most typically encountered in the Y reactant? (2pt) 6.5. Why does a pi-acceptor ligand serve to stabilize the intermediate in substitution at a square planar platinum center? (4pt) 7. Electron Transfer (10pt) 7.1. What is the defining feature of an inner-sphere ET reaction that differentiates it from an outer-sphere ET process? (2pt) 7.2. Electron transfer is (a) slow (b) fast relative to molecular vibrations of the nuclear framework. Pick one and give the name of this principle. (3pt) 7.3. Aqueous chromium(II) ion effects the one-electron reduction of [Co(NH3)5Cl]2+, after which the latter undergoes rapid hydrolysis, losing all of its ammonia ligands. Why is the cobalt complex stable to hydrolysis prior to reduction but unstable afterwards? (5pt) 3

Relevant Data: Periodic Table of the Elements 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

H

18

He

Li Be

B

C

N

O

F

Ne

Na Mg

Al

Si

P

S

Cl

Ar

Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Ac

As Sb Bi

Se Te Po

Br I At

Kr Xe Rn

K Rb Cs Fr

Ca Sr Ba Ra

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: D4h E

2C4 C2 2C'2 2C''2 I (z)

2S4

A1g A2g B1g B2g Eg A1u A2u B1u B2u

+1 +1 +1 +1 +2 +1 +1 +1 +1

+1 +1 -1 -1 0 +1 +1 -1 -1

Eu

+2 0

+1 +1 +1 +1 -2 +1 +1 +1 +1

+1 -1 +1 -1 0 +1 -1 +1 -1

-2 0

h

quadratic functions

cubic functions

+1 -1 -1 +1 0 -1 +1 +1 -1

linear functions, rotations Rz (Rx, Ry) z -

x2+y2, z2 x2-y2 xy (xz, yz) -

0

(x, y)

-

z3, z(x2+y2) xyz z(x2-y2) (xz2, yz2) (xy2, x2y), (x3, y3)

2

2

v

d

+1 -1 +1 -1 0 -1 +1 -1 +1

+1 -1 -1 +1 0 +1 -1 -1 +1

+1 +1 +1 +1 +2 -1 -1 -1 -1

+1 +1 -1 -1 0 -1 -1 +1 +1

+1 +1 +1 +1 -2 -1 -1 -1 -1

0

-2

0

+2 0

4

5.03 Syllabus and Lecture Plan - First Half of Spring, 2002 1. February 6 (Wednesday). Lecture Topic: Molecular Symmetry, Symmetry Elements and Operations. Reading: 3.1-3.2. 2. February 8 (Friday). Lecture Topic: Point Groups and assigning 3D objects to same. Reading: 3.3-3.4. 3. February 11 (Monday). Lecture Topic: Character Tables, reading them and understanding their constituent parts. Reading: 3.5-3.6 Also Appendix 3. 4. February 13 (Wednesday). Lecture Topic: Infrared Spectroscopy from a Symmetry point of view. Reading: 3.7-3.8 5. February 15 (Friday). Lecture Topic: Ligand Group Orbital approach to bonding in polyatomic molecules. Molecular orbitals for linear and bent XH2 systems. Reading: 4.1-4.4 Problem Set #1 due in class. Coverage is lectures 1-4 and associated readings 6. February 19 (Tuesday). Lecture Topic: Molecular orbitals for other simple polyatomic molecules. Reading: 4.5-4.7 7. February 20 (Wednesday). Lecture Topic: Structure and bonding in boron hydrides. Reading: 12.1-12.5, 12.11 8. February 22 (Friday). Lecture Topic: Nitrogen and Phosphorus Oxides: structure and bonding considerations. Reading: 14.8-14.11 9. February 25 (Monday). Lecture Topic: Structure and bonding for compounds of group 16 elements, particularly Sulfur. Reading: 15.1-15.4, 15.7-15.8, 15.10 Problem Set #2 due in class. Coverage is lectures 5-8 and associated readings 10. February 27 (Wednesday). Lecture Topic: Introduction to Coordination Chemistry. Reading: All of chapter 19. 11. March 1 (Friday). In place of Lecture 11 is Exam #1 in class . Coverage: lectures 1-9 and associated readings and problem sets 1 and 2. 12. March 4 (Monday). Lecture Topic: Crystal field splitting diagrams and CFSE. Reading: 20.1-20.3 13. March 6 (Wednesday). Lecture Topic: MO theory of complexes with pi-donor/acceptor ligands. Reading: 20.4 14. March 8 (Friday). Lecture Topic: Electronic spectra and Term Symbols. Reading 20.5-20.6 15. March 11 (Monday). Lecture Topic: Orgel and Tanabe-Sugano diagrams. Reading: 20.6 Problem Set #3 due in class. Coverage is lectures 10-14 and associated readings. 16. March 13 (Wednesday). Lecture Topic: Magnetic properties of Coordination Complexes. Reading: 20.8 17. March 15 (Friday). Lecture Topic: Ligand Substitution reactions in Square Planar complexes. Reading: 25.1-25.3 18. March 18 (Monday). Lecture Topic: Ligand Substitution reactions in Octahedral Complexes. Reading: 25.4 Problem Set #4 due in class. Coverage is lectures 15-17 and associated readings. 19. March 20 (Wednesday). Lecture Topic: Electron Transfer reactions. Reading: 25.5 Exam #2 this day in evening. Coverage is lectures 10-19 and associated readings and problem sets 3 and 4. 20. March 22 (Friday). Lecture canceled this day to make up for this week’s evening exam.

Syllabus for second half of 5.03; lectures by R. R. Schrock Lecture

Date

Topic

Reading

21

Apr 1, M

Alkyls of Groups 1, 2, 12, 13, and 14

18.1-18.5

22

Apr 3, W

Transition metal alkyls and hydrides

23

Apr 5, F

η -ligands

24

Apr 8, M

η -ligands and fluxional processes

23.13-23.15

25

Apr 10, W

Metal carbonyls and clusters

23.4

x x

23.2-23.3, 23.7, 23.9 23.10-23.11

Problem set #5 due in class 26 Patriot’s Day

Apr 12, F Apr 15

Multiple metal-ligand and metal-metal bonds

23.12, 22.7

No class.

27

Apr 17, W

Reactions at a transition metal center

23.7 (repeat)

28

Apr 19, F

Homogeneous catalysis

26.1-26.3

29

Apr 22, M

Homogeneous catalysis

26.1-26.3

Problem set #6 due in class 30

Apr 24, W

Exam III in class

31

Apr 26, F

Catalysis

26.4-26.6

32

Apr 29, M

Catalysis

26.4-26.6

33

May 1, W

Metals in Biology

28.1-28.5

34

May 3, F

Metals in Biology

28.1-28.5

Problem set #7 due in class 35

May 6, M

Metals in Biology

28.1-28.5

36

May 8, W

Solid State Chemistry

5.1-5.11, 5.17

37

May 10, F

Solid State Chemistry

27.1-27.4, 27.6

Problem set #8 due in class 38

May 13, M

Nuclear Chemistry

39

May 15, W

Lanthanides and Actinides

May 23, Thursday, Final Exam, 9 AM, Room 2-190

2.1-2.6, 2.8 24.1-24.3, 24.5-24.11