You are on page 1of 266

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 1 Date 2/6/02 Topic Symmetry Elements and Operations Point Group Assignments Character Tables IR Spectroscopy and Symmetry LGO's and MO's Simple MO's Boron Hydride Bonding N and P oxides Group 16 bonding Intro to Coordination Chemistry Exam #1 Crystal Field Theory Pi-donor/acceptor MO's Electronic Spectra Orgel and Tanabe-Sugano diagrams Lecturer CCC WRL* CCC CCC CCC CCC CCC CCC CCC CCC PDF PDF PDF PDF PDF PDF PDF PDF 3.3-3.4 3.5-3.6, Appendix 3 3.7-3.8 4.1-4.4 4.5-4.7 12.1-12.5, 12.11 14.8-14.11 15.1-15.4, 15.7-15.8, 15.10 Ch. 19 Lectures 1-9 and Readings PDF PDF PDF 20.1-20.3 20.4 20.5-20.6 Notes PDF 3.1-3.2 Readings

2 3 4 5 6 7 8 9

2/8/02 2/11/02 2/13/02 2/15/02 02/19/02 02/20/02 02/22/02 02/25/02

10

02/27/02

CCC

PDF

11

03/01/02

CCC

12 13 14

03/04/02 03/06/02 03/08/02

CCC CCC CCC

15

03/11/02

CCC

PDF

20.6

http://web.mit.edu/5.03/www/notes.html (1 of 3) [2002-05-14 20:25:12]

5.03 Syllabus and Lecture Notes

16

03/13/02

Magnetic Properties of Coord. compds. Ligand Subsitution: Square Planar Complexes Ligand Substitution: Octahedral Complexes

CCC

PDF

20.8

17

03/15/02

CCC

PDF

25.1-25.3

18

03/18/02

CCC

PDF

25.4

19 20 21

03/20/02 Electron Transfer 03/22/02 04/01/02 CANCELLED Alkyls of Groups 1, 2, 12, 13, and 14 Transition metal alkyls and hydrides ηx-ligands ηx-ligands and fluxional processes Metal carbonyls and clusters Multiple metal-ligand and metal-metal bonds Reactions at a transition metal center Homogeneous catalysis Homogeneous catalysis

CCC CCC RRS

PDF

25.5

PDF

18.1-18.5

22 23

04/03/02 04/05/02

RRS RRS

PDF PDF PDF

23.2-23.3, 23.7, 23.9 23.10-23.11

24

04/08/02

RRS

Ferrocene 23.13-23.15 MO's PDF 23.4

25

04/10/02

RRS

26

04/12/02

RRS

PDF

23.12

27

04/17/02

RRS

PDF

23.7 (repeat) 26.1-26.3 26.1-26.3

28 29 30 31 32 33

04/19/02 04/22/02

RRS RRS RRS RRS RRS RRS

PDF PDF

04/24/02 Exam #3 in class 04/26/02 04/29/02 05/01/02 Catalysis Catalysis Metals in Biology

PDF PDF PDF

26.4-26.6 26.4-26.6 28.1-28.5

http://web.mit.edu/5.03/www/notes.html (2 of 3) [2002-05-14 20:25:12]

5.03 Syllabus and Lecture Notes

34 35 36 37 38 39

05/03/02 05/06/02 05/08/02 05/10/02 05/13/02 05/15/02

Metals in Biology Metals in Biology Solid State Chemistry Solid State Chemistry Lanthanides and Actinides Nuclear Chemistry

RRS RRS RRS RRS RRS RRS

PDF PDF PDF PDF PDF PDF

28.1-28.5 28.1-28.5 5.1-5.11, 5.17 27.1-27.4, 27.6 Chapter 24 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: ahock@mit.edu Last updated: May 7, 2002

http://web.mit.edu/5.03/www/notes.html (3 of 3) [2002-05-14 20:25:12]

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: ahock@mit.edu Last updated: February 13, 2002 Initial concept by Tet Matsuguchi

http://web.mit.edu/5.03/www/index.html [2002-05-14 20:25:14]

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]

-Adam 03/13/02: pset #3 solutions are up! 03/12/02: pset 4 is up. 2.9.13 03/05/02: Problem Set #3 is up! -Adam 02/26/02: I forgot to announce it.mit. Also.SD for pset 1. 02/06/02: The syllabus page should be updated with the http://web. Cummins will have extra office hours this week R 3-4 and F 11-12. Amrit's extra office hours/review session will be R 4-?. and a link to the one I use is included. so check back! Amrit will hold extra office hours R 4-?. Come and see what all the fuss is about Thursday at 5. -Adam 02/26/02: Adam will hold extra office hours W 2-4. -Adam 03/05/02: FYI.edu/5. -Adam 02/19/02: Amrit and Adam's office hours are moved to room 2-131. though. 03/11/02: Prof. but it will most likely not be returned in time for you to study for the test.03/www/announcements. the avg +/.03 Announcements the exam from your work. location TBA. and the exam were: pset1: 39 +/. The solutions will be posted the afternoon the pset is due. -Adam 02/26/02: The 3-D molecule files Amrit and I showed in recitation are online in the notes section. the P. -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. 1 key is posted -Adam 02/17/02: P. The links to the notes go to blank spots at the momment. location TBA. -Adam 02/12/02: Recitation#5 is permantly moved to room 2-135. but the solutions to pset #2 have been posted since this afternoon.6 Exam1: 47 +/.8 pset2: 29 +/.html (2 of 3) [2002-05-14 20:25:15] . 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. also in 8-119.5.S. -Adam 02/26/02: Adam's EXTRA office hours/review session will be W 2-4 in 8-119.S. You will have to download a VRML viewer.

1's due date.html (3 of 3) [2002-05-14 20:25:15] .edu Last updated: May 7.5.03 Announcements correct lecture topics up to P.edu/5.mit. 2002 http://web.S.edu 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: ahock@mit.03/www/announcements. All PS due dates are correct through exam #2 on the calender page (as far as I know! email me at ahock@mit.

Room 2-204. Room 2-105 Instructors Teaching Assistants Administration: Kris Grabarek. grabarek@mit. Course Manager. 2001) ISBN 0582-31080-6 Other books that may prove useful (on reserve in 14N-132): Recitations Recitation sections are assigned by the registrar. Housecroft and Sharpe (Prentice Hall. Education. There will be three lectures per week and one recitation section devoted to discussion of the assigned problems and lecture material.html (1 of 3) [2002-05-14 20:25:15] .edu Jennifer Picray. jlpicray@mit.edu/5. Assistant Director of Chem. 10:05AM-10:55AM.03 Information Spring Term 2002 5.edu Textbook: Inorganic Chemistry.03 Inorganic Chemistry I This subject deals primarily with chemical bonding and molecular structure. x3-0909. Room 2-204.mit. Changes to assigned recitations will be made in the Chemistry Education Office (in person only.5. Web Manager. x8-7492.edu Laura Howe. lhowe@mit. http://web. Lectures: MWF.03/www/information. and their application to the chemistry of representative elements of the periodic system. no changes will be made by phone or e-mail). Room 2-204. x3-7271.

Academic Honesty It is expected that students will maintain the highest standards of academic honesty. or difficult-to-decipher work will not be graded.03/www/information.edu/5. Following a test or examination. (2) represent the work of another student as his or her own.03 Information Grading: There will be a total of 1000 points for the semester. In advance of a test or exam. including suspension and expulsion. it is expected that no student will turn in work that is not his or her own. can be imposed. Copy over your work prior to turning it in if necessary.5. Such departures are considered serious offenses for which disciplinary penalties. a student will not try to deceive teachers or graders by misrepresenting or altering his or her previous work. Copying of other students work is not permitted. (3) use aids to memory other than those expressly permitted by the examiner.html (2 of 3) [2002-05-14 20:25:15] . a student will not knowingly obtain access to the exam questions.mit. messy. It is expected that during a test or examination. With respect to homework assignments. Full credit will not be awarded for answers only: remember to show your work! Illegible. a student will not (1) accept or use information of any kind from other students. http://web. Departures from the above standards are contrary to fundamental principles of MIT and of the larger scientific community. The distribution for the first half may be found here.

2002 http://web.mit.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: ahock@mit.03/www/information.5.edu/5.html (3 of 3) [2002-05-14 20:25:15] .edu Last updated: February 6.

Room 2-204.edu Office Hours: R 5-6 R 5-6 2-131 2-131 2-139 Adam 2-132 Amrit 1-134 Adam 1-134 Amrit 2-135 Adam 2-136 Amrit Administration: Kris Grabarek. Room 2-204.03 Faculty and Staff Instructors: Prof. TW in 2-227 Cummins Prof. Course Manager.edu http://web. Web Manager.edu Teaching Assistants: Adam Hock Amritanshu Sinha Recitations: Rec # Time Room 1 2 3 4 5 6 W9 R2 R1 T1 T10 M1 TA ahock@mit.html (1 of 2) [2002-05-14 20:25:16] .03/www/staff. x3-0909. jlpicray@mit. Richard R.5. x3-7271.edu Laura Howe.edu Jennifer Picray. Room 2-204. Assistant Director of Chem. ccummins@mit.edu Christopher 2-227 x3-5332 Office Hours: 3-4 C. x8-7492.mit. Education. Schrock 6-331 x3-1596 rrs@mit. grabarek@mit.edu/5.edu asinha@mit. lhowe@mit.

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: ahock@mit. 2002 http://web.html (2 of 2) [2002-05-14 20:25:16] .03/www/staff.edu/5.edu Last updated: February 19.mit.

2002 Monday Tuesday Wednesday Thursday Friday 1 Lecture 11 Exam #1 in class Room TBA http://web.mit.03/www/calendar. 2002 Monday Tuesday Wednesday Thursday 1 4 Registration Day 5 6 Lecture 1 Symmetry Elements and Operations 7 8 Lecture 2 Point Group Assignments Friday 11 Lecture 3 Character Tables 12 13 14 Lecture 4 IR Spectroscopy and Symmetry 15 Lecture 5 LGO's and MO's Problem Set #1 Due in class 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 Problem Set #2 Due in class 26 20 21 Lecture 7 Boron Hydride BondingPDF 27 28 Lecture 10 Intro to Coordination Chemistry PDF March.html (1 of 4) [2002-05-14 20:25:17] .edu/5.5.03 Course Calendar Course Calendar February.

03/www/calendar. 12.5.03 Course Calendar 4 Lecture 12 Crystal Field Theory PDF 5 6 7 Lecture 13 Pi-donor/acceptor MO's PDF 8 Lecture 14 Electronic Spectra PDF Add Date 15 Lecture 17 Ligand Subsitution: Square Planar Complexes PDF 22 Lecture 20 Cancelled due to the exam 3/20.mit. PDF 14 20 21 Lecture 19 Electron Transfer PDF Exam #2 Evening Exam 7:30 PM in 2-190 27 28 29 April. compds.edu/5. 13. and 14 PDF 8 Lecture 24 ηx-ligands and fluxional processes PDF 9 11 12 Lecture 26 Multiple metal-ligand and metal-metal bonds PDF http://web. 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 13 Lecture 16 Magnetic Properties of Coord. 2. 2002 Monday Tuesday Wednesday 3 Lecture 22 Transition metal alkyls and hydrides PDF 10 Lecture 25 Metal carbonyls and clusters PDF Problem Set #5 Due in class Thursday 4 Friday 5 Lecture 23 ηx-ligands PDF 1 2 Lecture 21 Alkyls of Groups 1.html (2 of 4) [2002-05-14 20:25:17] .

03/www/calendar. 2002 Monday Tuesday Wednesday 1 Lecture 33 Metals in Biology PDF 2 Thursday 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 14 15 Lecture 39 Nuclear Chemistry 16 17 http://web.5.mit.html (3 of 4) [2002-05-14 20:25:17] .edu/5.03 Course Calendar 15 Patriot's Day Holiday 16 Patriot's Day Holiday 17 Lecture 27 Reactions at a transition metal center PDF 24 Lecture 30 Exam #3 in class 18 19 Lecture 28 Homogeneous catalysis PDF 22 23 Lecture 29 Homogeneous catalysis PDF Problem Set #6 Due in class 29 30 Lecture 32 Catalysis PDF 25 Drop Date 26 Lecture 31 Catalysis PDF May.

5.edu Last updated: May 1.html (4 of 4) [2002-05-14 20:25:17] .03 Course Calendar 20 21 22 23 Final Exam 9:00 AM in 2-190 24 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: ahock@mit.mit.edu/5.03/www/calendar. 2002 http://web.

edu Last updated: May 6.03 Assignments Problem sets are due in class on the due date. 2002 http://web. Problem Set 1 2 3 PDF PDF PDF Due 02/15/02 02/25/02 03/11/02 Solutions PDF PDF PDF PDF 4 PDF* 03/18/02 fixed pg 3 PDF PDF 5 6 7 8 * PDF PDF PDF PDF 04/10/02 04/22/02 05/03/02 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: ahock@mit.mit.5.edu/5.03/www/assignments.html [2002-05-14 20:25:18] .

03 Exams All Examinations will be closed-book and closed notes.mit. Exam Exam I Exam II* Exam III Exam IV Final *Exam II is at 7:30 pm! Date 03/01/02 03/20/02 TBA TBA TBA Room TBA 2-190 TBA TBA TBA Info PDF PDF Solutions PDF PDF Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources Department of Chemistry Send comments and suggestions to course webmaster: ahock@mit.edu Last updated: April 4.5.edu/5.html [2002-05-14 20:25:19] . 2002 http://web.03/www/exams.

edu Last updated: April 21.Are you Course 5? Interested in Chemistry? Join ClubChem! Faculty Dinners. Character Table (at the bottom!).The name speaks for itself.03/www/resources. Chemistry Sites: Organometallic Hypertextbook . Club Chem .mit.03 Resources Getting Textbooks Textbooks are available at several bookstores on-line as well as at the COOP. compounds. 2002 http://web. Announcements | General Information | Faculty and Staff | Calendar | Syllabus and Lecture Notes | Assignments | Exams | Resources Department of Chemistry Send comments and suggestions to course webmaster: ahock@mit. Getting Help Tutoring is available from the Tutoring Services Room (TSR) of the Office of Minority Education.The first periodic table on the WWW. etc. pictures. It also has a large amount of information about each individual element such as its history. etc. uses. Call TSR at x3-8406 any day after 2pm.html [2002-05-14 20:25:22] . MIT Chemistry Department WebElements Periodic Table .5. and presents the theory that culminates in character tables.edu/5. Chemistry Magic Shows.Handy if you are ever caught without a copy of a chemist's best friend! This is a math site.

g. where G is the number of boxes and N the number of equivalent spin ½ particles you can place in those boxes applies. ligand. etc. and work through your choice (iv) determine the total degeneracy of the ground configuration. (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. Note: degenerate energy levels may not include all microstates that exist in K symmetry. Determine the local point group symmetry as in pset #1 by disregarding H's on water.Analyze the each of the following complexes as follows: (i) determine the correct local point group symmetry based on the environment at the metal. the highspin versus the lowspin form. but considering ligand denticity and geometry. The formula G!/(N!* (G-N)!). (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. etc) that lead the system to adopt e. 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 . (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.

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. Spring 2002.03. 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 .

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

7c.03 Problem Set #1.1. or difficult-to-decipher work will not be graded.9b.5a. 18.25 . 16. 3.in each case draw a schematic for the flow of logic that led you to your point group assignment.2.4. 3. Spring 2002.5a.9a from your textbook -. 1. February 15 Policy Statement: because this is a graded problem set it is expected that each student will do his/her own work. 3.4. 18.12. Draw and assign to their proper point groups the molecules depicted in figures 17. Find the symmetry species (also called Mulliken Symbols or irreducible representations) for the normal modes of water. Assume the water molecule to lie in the Cartesian yz plane and match the normal mode symmetries with their pictures in figure 3. 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.9a. 18.5d. Full credit will not be awarded for answers only: remember to show all your work! Illegible. 18. 3. 19. (10 points) 3. As in the preceding problem but using the D(4h) character table for [PtCl4]2. (10 points) 4.8.and the diagram in figure 3.4a.23. 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. (17 points) 2. 16. 19. Use each of the s.g. 18.5b. 19. 3. 19. and d atomic orbitals (nine orbitals total!).5.14c. Due in class on Friday.7c. (13 points) Additional study problems (not graded but helpful for the exam) from page 90: 3.5a. using the C(2v) character table. 18.14 on page 86. 3. 17.21.4c.7b. 18. 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.3a. 19.6a. p. messy. 3. Copy over your work prior to turning it in if necessary. Draw each orbital (labeled e. 16.11 on page 84.

.

.

.

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).

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

Consider this in C(2v) symmetry.12 and the corresponding Crystal field view of the same situation.10 of your textbook. 20. comment on the likely origin of any discrepancies. 19. Provided a succinct yet complete definition of each of these terms.5.18. Solve them. 19. 4. and populated with the correct number of electrons in each case. 3. with sigma-only donor ligands. Give corresponding Crystal field splitting diagrams.5. 6. consider a nickel(II) complex with a single carbon monoxide ligand included in a square-planar arrangement of ligands.3. 8. 19. 5. and 3. 20. fully labeled with symmetry labels. 2. 20. a complete yet succinct definition for each one of these terms. Find the oxidation state.12.1. 19. Explain in your own words what the relationship is between the figure of figure 20. Be sure to label all orbitals in both diagrams with the appropriate symmetry label (Mulliken label). .2. On page 476 of your textbook you will find self-study exercises 1. in your own words. showing which d orbital (s) goes to lower energy vis-a-vis the D(4h) parent complex.8.11.4 on page 464 of your textbook.9. Now. 19.15.12.3. A list of terms is provided on page 485 of your textbook. derive the splitting diagrams pictured in figure 20. 20. Consider the Crystal field splitting diagrams for a nickel(II) complex in D(4h) symmetry.8.7. Do your derivations differ in any substantial respect with the results pictured in the text? If so. On page 486 of your textbook you will find problems 20.6. using your own words. and group in the periodic table for the metal in each molecule depicted in figures 19. Using the methods and concepts introduced in the Monday March 4 lecture. recollecting the MO picture in box 20. on page 460. 2. 19. number of d electrons. and also in problem 19. 20. 20. 7. Give. On page 450 of your textbook is given a list of terms introduced in the chapter.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

a2 u* e2 g* a1 g* e2 u e 1 g* a1 g e2 g e1 u e1 g a2 u a1 g .03 Problem Set #5 Due 4/10/02 1.6a.) Explain the following and show the occupancy of the MO's in the diagram for parts (a) . (b) Cr(η5-C 5 H5 )2 has two unpaired electrons.5 points each) (a) Textbook problem 18. but less consequential in most circumstances.) (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. (The ordering of the higher levels is also uncertain. (Look at and think about Table 18. Explain why this is the case. (c) Ni(η5-C 5 H5 )2 has two unpaired electrons. A qualitative molecular orbital diagram for a metallocene is shown to the right. (15 points total.(d): (a) V(η5-C 5H5) 2 is a violet paramagnetic solid. Note that the ordering of the levels within the dashed box is not correct for all metallocenes. 2.6b. (d) Co(η5-C 5H5) 2 can be oxidized readily to {Co(η5-C 5 H5 )2}+. (c) The reactivity of LiR compounds in a given solvent such as diethyl ether follows the order R = Me < n-butyl < t-butyl. (b) Textbook problem 18. Explain the increase in reactivity in terms of the structures of LiR Compounds that are likely to be present in each case. ethyllithium in pentane.5 each) Metallocenes and related species are ubiquitous in organotransition metal chemistry. on the basis of certain facts such as the number of unpaired electrons. Where would one expect to observe a transition metal hydride resonance in a proton NMR spectrum? e1 u* O O O O benzo-12-crown-4 (e) Explain why W(CH2 CH3 )6 is unlikely to be prepared by treating WCl6 with six equivalents of 2. 2. (20 pts.1.1 5. (f) Explain why ethylation of a transition metal species is sometimes the way to prepare a metal hydride complex.

Draw this structure and rationalize why it is an 18e species.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. (Dissociation of ethylene can be excluded by other experiments. (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.) (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. Explain in orbital terms why η5-C 5H5 bonding might be weak in the p-block elements versus the transition metals. (f) Although η 5-C 5H5 compounds are known for main group elements (see chapter 18). Provide two or more reasons why that might be the case. in [Pb(η 5-C 5H5 )2 ]n is usually relatively weak.) . At high Ho Hi Rh Hi Ho Ho Hi Hi Ho temperatures only one singlet of area eight is observed for these protons.. Explain why this is the case. (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 the resonance for the η 1-C 5H5 ligand is a sharp singlet. (15 pts total. (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.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. η5-C 5 H5 bonding in p-block elements (e. At low temperatures two complex resonances are observed for the Hi and Ho protons. (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. Explain what is happening at high temperatures that leads to "equilibration" of the Hi and Ho protons. each with area 4. (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.g. 2.

+ 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 not in orbital terms. 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.3 (e) η3-C 3H5 ligands do not rotate without a barrier about the axis shown in the platinum complex shown below. . Explain why.

.

.

.

.

.

xy). (15 points total) Dicobalt octacarbonyl can take the two forms (A and B).03 Problem Set #6 Due 4/22/02 53 points total 1. Ry ) (x2 . and d orbitals in the D4h point group and construct and discuss an MO scheme that describes the bonding in hypothetical biscyclobutadiene iron.y) Rz (Rx . (c) (2 pts) Would you expect hypothetical biscyclobutadiene iron to be a stable species at 22°C? Why or why not? 2. O C Co C O A D3d A1g A2g Eg A1u A2u Eu E 1 1 2 1 1 2 2C3 1 1 -1 1 1 -1 3C2 1 -1 0 1 -1 0 i 1 1 2 -1 -1 -2 2S 6 1 1 -1 -1 -1 1 3σd 1 -1 0 -1 1 0 z (x. eclipsed cyclobutadiene rings that ultimately will receive an iron atom between them to form currently unknown biscyclobutadiene iron (D4h symmetry). which have C2v and D3d symmetries. (xz.y2 . (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. assuming that the Co-C-O bond angles are 180°.1 5. (b) (5 pts) Look up the symmetries of the s. (12 points total) Consider two parallel. respectively. yz) z2 Co OC OC Co OC OC B OC CO Co CO CO OC OC OC CO CO CO . p.

and state on that basis how many CO stretches could in theory be observed in the IR spectrum of B. and explain why. reduce it. write down the representation for the eight CO stretches (arrows) in molecule B. Explain why this is the case. (c) Predict whether ν CO will be higher or lower in energy in compound A vs. a "Fischer Carbene" complex. You can see by inspection that two IR active bridging CO stretches would be observed in A. compound B and explain why. and prove that they are both IR active. write a representation for the two bridging CO stretches in A.2 (a) (5 pts) Assume that the CO stretches can be isolated from the rest of the atomic displacements in the molecule. On this basis which structure must Co2 (CO)8 have? 3. (Note that BH 3 is purely a Lewis acid. Nevertheless. reduce it to a sum of irreducible representations. + F3P F3P Fe CO A Me3P Me3P Fe CO B + (d) In (CO)5Cr=C(C 6H5)(NMe2).) (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 that four CO stretches are observed experimentally in the region between 1700 and 2000 cm-1. (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? . 2 each) (a) When CO coordinates (weakly) to BH 3 its stretching frequency actually increases. (Why?) Therefore the bridging CO stretches in molecule A can be analyzed separately. the methyl groups on the nitrogen atom are inequivalent on the NMR time scale at low temperature in the proton NMR spectrum. (b) (3 pts) Bridging CO stretches are observed at lower energies than terminal CO stretches. (d) (2 pts) Assume that Co2 (CO)8 has either one form or the other. Using an arrow between each C and O as an indicator of a CO stretch. (10 pts total. Explain why. (c) (5 pts) Go through the same exercise to analyze the six terminal CO stretches in molecule A.

or 6. 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. in the plane of the paper). Only three frontier orbitals are available for forming three bonds to ligands. such as the one shown in the Zr compound shown in (e) normally bind to a metal to give a "pseudo triple bond. draw views from the "side" or "front" (with the Cp's going into the page).. A is a dz2-like orbital. (16 points total) "Bent" biscyclopentadienyl complexes are found for metals in groups 4. as well as from the "top". 5. Why not? .e. (b) (2 pts ) Cp2 WCl2 ." Why is that not possible in this circumstance. (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 a rotation is not possible for orbital reasons in this circumstance. (If necessary. as shown below.3 4.) + Cp + Cp Cp + B C Cp Cp Cp A (a) (2 pts ) Cp2 TaH3 . The orbitals are shown below. Show how these orbitals are used in the following circumstances and describe and draw the structure of each species unambiguously. (Orbital A can also be empty or can contain a lone pair.) Note that all three orbitals lie in the plane that passes between the two cyclopentadienyl ligands (i.

.

.

.

.

.

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 toluene OMe

(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

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. [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 O Mo O O-t-Bu t-Bu Ph
catalyst

N

i-Pr

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 N

Me Me

O

Mo Me

Ph

O

1 mo l % c atalys t
O Me Me

Me H Me O

- C 2H 4 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 Fe (porph)N RH + 2 H + + 2e + O2 N(porph) H 2O + ROH N(porph)

(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. Illegible work will not be graded. it is advisable to maximize your points by first attempting those questions that are relatively easy and/or carry more points. therefore. Good Luck! Relevant data are provided on the last two pages. 1 . Please answer all questions in the blue books provided. Please read through the entire paper (total 4 pages) before beginning to answer the problems.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. You have 90 minutes for this exam.

Electronic transitions for [PtCl4]2.1. explain why there is a stabilization associated with the chromium(III) ion in an octahedral field. In octahedral symmetry? (3pt) 4. MO Theory of Complexes with Inclusion of Pi Bonding (17pt) 1.4.1. (8pt) 2. (9pt) 4. Ti3+) in spherical symmetry? (3pt) 4. Indicate for which of the three the energy of the T2g set is at a maximum. Werner’s proof of the coordination theory relied most heavily on what physical property of octahedral metal complexes? (3pt) 2. (4pt) 1. and draw a schematic MO diagram illustrating why. Mo(NMe2)6.5.4. Why is it rare to encounter a low-spin tetrahedral coordination complex? (6pt) 2.1. Orgel Diagrams (28pt) 4. For an octahedral metal complex. (4pt) 2. What is the ground term for [PtCl4]2-? (5pt) 4.3.3.6. Term Symbols.3.6. What is the ground term for a d1 ion in tetrahedral symmetry? (4pt) 4. Draw the three coordination polyhedra that are typical of coordination number seven. 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.5. Neglecting the effects of charge and assuming sigma effects to be the same.2. Which the smallest? Very briefly explain your choice. (4pt) 1. or [Mo(NH3)6]3+? Very briefly explain your choice. What dn configuration is found most commonly for an octahedral metal complex of cobalt? (2pt) 1. What is the spin multiplicity in the latter (tetrahedral) case? (2pt) 4.2.5. (4pt) 2. Coordination Chemistry – general (20pt) 1. (9pt) 1.2.3. Calculate the CFSE for [Cr(OH2)6]3+ and illustrate schematically how you calculated this quantity.1.will be spin-allowed if the excited states have what spin multiplicity? (2pt) 2 . (4pt) 1. which of the metal d orbitals are involved in sigma bonding to the ligands? (2pt) 2. What is the total degeneracy (number of microstates) for a d1 ion (e. Crystal Field Theory (32pt) 2. (8pt) 3.g.1. Define the term “linkage isomerism” with the help of an example. From a physical point of view based on the CF model. which ligand would you choose: chloride or cyanide? Explain your choice.2. What dn configuration is found most commonly for a square planar platinum complex? (2pt) 1. If you were to attempt to synthesize a low-spin tetrahedral complex.4. which of the following is expected to have the largest value of ∆o: Mo(CO)6.

6. which are most consistent with the latter observation: D. losing all of its ammonia ligands. What are the quantities correlated in an Orgel diagram and as a function of what are they correlated? (3pt) 5. Why is the cobalt complex stable to hydrolysis prior to reduction but unstable afterwards? (5pt) 3 .4. Retention of stereochemistry for substitution at square-planar platinum is indicative of an (a) associative or (b) a dissociative pathway? Explain your choice. (6pt) 4. and rather seem to depend mainly on the nature of the leaving group.4. Indicate which. (5pt) 6. (8pt) 6. Electron Transfer (10pt) 7. (b) MLCT bands.3.7.4. What is the name of this effect and what is its origin in MO terms? (6pt) 6. The complex [Co(OH2)6]2+ exhibits a µeff greater than that predicted by the spinonly formula. Chloride opposite chloride is substituted more readily than chloride opposite ammonia. Ligand Substitution (25pt) 6.3. What is the defining feature of an inner-sphere ET reaction that differentiates it from an outer-sphere ET process? (2pt) 7. in a square planar complex.2. what is the order most typically encountered in the Y reactant? (2pt) 6. Why does a pi-acceptor ligand serve to stabilize the intermediate in substitution at a square planar platinum center? (4pt) 7. In the rate law for the reaction ML5X + Y à ML5Y + X.5. Pick one and give the name of this principle.5. A Curie paramagnet exhibits a linear relationship between the temperature and what quantity? (2pt) 1.1. Liquid oxygen (which incidentally is blue) is (a) attracted into (b) repelled away from a magnetic field. What is the spin-only value of µeff expected for [Cr(NH3)6]Br2 if the complex is high-spin? (3pt) 1.8. Aqueous chromium(II) ion effects the one-electron reduction of [Co(NH3)5Cl]2+. The spin multiplicity of the ground term for dioxygen is what? (2pt) 6. and explain.3. (5pt) 1. A? Explain your choice(s).2. Explain the origin of this effect. Electron transfer is (a) slow (b) fast relative to molecular vibrations of the nuclear framework. Ia. after which the latter undergoes rapid hydrolysis. (3pt) 1.2.1. Magnetic Properties (18pt) 1.1. An Orgel diagram can be referred to also as a correlation diagram. intense color of [Ru(bpy)3]2+ is due to (a) d-d bands. Id. Rates of ligand substitution in octahedral cobalt and chromium systems typically are invariant with respect to the nature of the entering ligand. Explain your choice. Of the following mechanistic alternatives. If it is low-spin? (3pt) 1. (3pt) 7. The characteristic.

Relevant Data: Periodic Table of the Elements 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 H Li Be Na Mg K Rb Cs Fr Ca Sr Ba Ra B Al C Si N P As Sb Bi O S Se Te Po F Cl Br I At He Ne Ar Kr Xe Rn 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 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Th Pa U Np Pu Am Cm Bk Cf Es Er Fm Tm Yb Md No Lu Lr Character tables: D4h E A1g A2g B1g B2g Eg A1u A2u B1u B2u Eu +1 +1 +1 +1 +2 +1 +1 +1 +1 2C4 C2 2C'2 2C''2 I (z) +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 0 +1 -1 -1 +1 0 +1 +1 +1 +1 +2 -1 -1 -1 -1 -2 2S4 +1 +1 -1 -1 0 -1 -1 +1 +1 0 2 h v 2 d +1 +1 +1 +1 -2 -1 -1 -1 -1 +1 -1 +1 -1 0 -1 +1 -1 +1 +1 -1 -1 +1 0 -1 +1 +1 -1 0 linear functions. yz2) (xy2. yz) - cubic functions z3. Ry) z (x. x2y). (x3. y3) +2 0 -2 0 +2 0 4 . z2 x2-y2 xy (xz. z(x2+y2) xyz z(x2-y2) (xz2. y) quadratic functions x2+y2. rotations Rz (Rx.

.

.

.

.

.

.

.

.

Lecture Topic: Molecular Symmetry.1-3. Lecture Topic: Electronic spectra and Term Symbols.4 Problem Set #1 due in class. February 25 (Monday).5 Exam #2 this day in evening. 12.8-14.1-25. Coverage: lectures 1-9 and associated readings and problem sets 1 and 2.8 17. February 13 (Wednesday). Lecture Topic: Structure and bonding in boron hydrides.3 13. 20. February 11 (Monday).5-4. 15. Reading: 25.4 14. 16.7-3.1-20. March 6 (Wednesday).5. February 27 (Wednesday). February 19 (Tuesday). Reading: 15. February 6 (Wednesday). Reading: 3. Lecture Topic: Molecular orbitals for other simple polyatomic molecules. particularly Sulfur. Lecture Topic: MO theory of complexes with pi-donor/acceptor ligands. Symmetry Elements and Operations.5-3. Reading: 12. March 4 (Monday). 3. 4. reading them and understanding their constituent parts.5-20. Lecture Topic: Introduction to Coordination Chemistry. Coverage is lectures 1-4 and associated readings 6. February 8 (Friday). March 15 (Friday). Lecture Topic: Character Tables. Coverage is lectures 5-8 and associated readings 10. February 22 (Friday). February 15 (Friday). March 1 (Friday). Lecture Topic: Nitrogen and Phosphorus Oxides: structure and bonding considerations.7-15. Coverage is lectures 15-17 and associated readings. March 13 (Wednesday). In place of Lecture 11 is Exam #1 in class . Reading: 4.3 18. 2. Coverage is lectures 10-14 and associated readings. Lecture Topic: Ligand Substitution reactions in Octahedral Complexes. Lecture Topic: Infrared Spectroscopy from a Symmetry point of view. Lecture Topic: Crystal field splitting diagrams and CFSE.4 Problem Set #4 due in class. . Lecture Topic: Structure and bonding for compounds of group 16 elements.3-3.11 9. Reading: All of chapter 19.1-15. 11.First Half of Spring. Lecture canceled this day to make up for this week’s evening exam. Lecture Topic: Ligand Group Orbital approach to bonding in polyatomic molecules. Coverage is lectures 10-19 and associated readings and problem sets 3 and 4. March 20 (Wednesday). March 11 (Monday). 19.03 Syllabus and Lecture Plan .6 15. March 22 (Friday).1-12. Reading: 4.11 8. Reading: 20. 2002 1.7 7. Lecture Topic: Electron Transfer reactions. Reading: 3. March 18 (Monday).8 5. March 8 (Friday). 12. Reading: 3. Lecture Topic: Magnetic properties of Coordination Complexes.1-4. Reading 20. February 20 (Wednesday). 15. Lecture Topic: Point Groups and assigning 3D objects to same. Lecture Topic: Ligand Substitution reactions in Square Planar complexes. Reading: 14.2. Lecture Topic: Orgel and Tanabe-Sugano diagrams. Reading: 20.6 Also Appendix 3. Reading: 20.10 Problem Set #2 due in class. Reading: 25. Molecular orbitals for linear and bent XH2 systems.4. Reading: 20.8.5. Reading: 25.6 Problem Set #3 due in class. Reading: 3.4.

2-23. 12. M Apr 10. Final Exam.4-26. F Apr 29. and 14 Transition metal alkyls and hydrides η -ligands η -ligands and fluxional processes Metal carbonyls and clusters Problem set #5 due in class 26 Patriot’s Day 27 28 29 Apr 12.6 26. F Apr 15 Apr 17.1-26. Schrock Lecture 21 22 23 24 25 Date Apr 1. F Metals in Biology Solid State Chemistry Solid State Chemistry Problem set #8 due in class 38 39 May 13. W Nuclear Chemistry Lanthanides and Actinides 2.5-24. W May 10.4 May 23.1-28.Syllabus for second half of 5.6 28.5 23.4.17 27.11. 2. W May 3. Reactions at a transition metal center Homogeneous catalysis Homogeneous catalysis Problem set #6 due in class 30 31 32 33 34 Apr 24.3 26. 13. W Apr 5.8 24.12.5 28.1-18. 27.1-27. 23. M Multiple metal-ligand and metal-metal bonds No class. R. M May 1.1-26.15 23. Thursday. Room 2-190 .6 26.3. F Exam III in class Catalysis Catalysis Metals in Biology Metals in Biology Problem set #7 due in class 35 36 37 May 6.1-28. 5.4-26. 2.1-28.1-2.7.5 5.11 23. 24. W Apr 19.1-5. W Apr 26.1-24. M Apr 3. W Topic Alkyls of Groups 1.9 23.03.7 (repeat) 26.10-23.3 23. 23.5 23. lectures by R. F Apr 8. 9 AM. F Apr 22. M May 8.13-23.3.11 28. M May 15. 22.7 x x Reading 18.6.