inorganic chemistry mit lecture notes

Syllabus and Lecture NotesThe syllabus is available here (updated!). The point distribution for the firsthalf of the semester is here.

The schedule below will be updated with notes, figures, and readings fromlectures.

*The wrl files require a VRML viewer. Cosmoplayer is one that works withnetscape and internet explorer.

Lecture Date Topic Lecturer Notes Readings

1 2/6/02Symmetry

Elements andOperations

CCCPDF

WRL*3.1-3.2

2 2/8/02Point GroupAssignments

CCC PDF 3.3-3.4

3 2/11/02 Character Tables CCC PDF 3.5-3.6,Appendix 3

4 2/13/02IR Spectroscopyand 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 02/20/02Boron Hydride

BondingCCC PDF 12.1-12.5,

12.11

8 02/22/02 N and P oxides CCC PDF 14.8-14.11

9 02/25/02Group 16bonding

CCC PDF15.1-15.4,15.7-15.8,

15.10

10 02/27/02Intro to

CoordinationChemistry

CCC PDF Ch. 19

11 03/01/02 Exam #1 CCCLectures1-9 and

Readings

12 03/04/02Crystal Field

TheoryCCC PDF 20.1-20.3

13 03/06/02Pi-donor/acceptor

MO'sCCC PDF 20.4

14 03/08/02Electronic

SpectraCCC PDF 20.5-20.6

15 03/11/02Orgel and

Tanabe-Suganodiagrams

CCC PDF 20.6

5.03 Syllabus and Lecture Notes

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

http://www.cai.com/cosmo/

http://web.mit.edu/5.03/www/handouts/pointgroups.zip

16 03/13/02Magnetic

Properties ofCoord. compds.

CCC PDF 20.8

17 03/15/02

LigandSubsitution:

Square PlanarComplexes

CCC PDF 25.1-25.3

18 03/18/02

LigandSubstitution:OctahedralComplexes

CCC PDF 25.4

19 03/20/02 Electron Transfer CCC PDF 25.5

20 03/22/02 CANCELLED CCC

21 04/01/02Alkyls of Groups1, 2, 12, 13, and

14RRS PDF 18.1-18.5

22 04/03/02Transition metal

alkyls andhydrides

RRS PDF 23.2-23.3,23.7, 23.9

23 04/05/02 ηx-ligands RRS PDF 23.10-23.11

24 04/08/02ηx-ligands and

fluxionalprocesses

RRS

PDF

FerroceneMO's

23.13-23.15

25 04/10/02Metal carbonyls

and clustersRRS PDF 23.4

26 04/12/02

Multiplemetal-ligand and

metal-metalbonds

RRS PDF 23.12

27 04/17/02Reactions at a

transition metalcenter

RRS PDF 23.7(repeat)

28 04/19/02Homogeneous

catalysisRRS PDF 26.1-26.3

29 04/22/02Homogeneous

catalysisRRS 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 05/01/02Metals inBiology

RRS PDF 28.1-28.5




RRS PDF 28.1-28.5


RRS PDF 28.1-28.5

36 05/08/02Solid StateChemistry

RRS PDF 5.1-5.11,5.17

37 05/10/02Solid StateChemistry

RRS PDF 27.1-27.4,27.6

38 05/13/02Lanthanides and

ActinidesRRS PDF Chapter 24

39 05/15/02Nuclear

ChemistryRRS PDF Chapter 2

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



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http://web.mit.edu/chemistry

mailto:[email protected]

Spring 2002MWF10 2-105

Prof. Christopher C.Cummins

Prof. Richard R.Schrock

Presents principles of chemical bonding and molecularstructure, and their application to the chemistry of representative

elements of the periodic system.

---

Welcome to 5.03.

Check the Announcements pagefor page update information.

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

Department of ChemistrySend comments and suggestions to course webmaster: [email protected] updated: February 13, 2002

Initial concept by Tet Matsuguchi

5.03 Course Home Page

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

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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 remainderof 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 inclass

04/23/02: PS 5 will be in the chem ed office as of 8:30 am orso. 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, pleasenote that lecture 27,28, and 29 are up and that 27 wasincorrectly iin 28's place. Everything is correct now, though.Happy studying!

04/21/02: This link has been added to the resorces page, andyou may find it useful.

04/21/02: There will be a review session for exam 3 onTuesday the 23rd at 1:00 in room 1-134

04/21/02: The MO's of ferrocene have been posted on thenotes page.

04/08/02: Please note: Problem 3f of pset#5 should have a4:1 ratio of H's

03/30/02: Welcome back! We hope everyone had awonderful spring break.

03/30/02: pset #5 is up!

03/30/02: The syllabus, calender, and assignments have beenupdated with information about the second half of thesemester. -Adam

03/18/02: Adam and Amrit will have extra office hours tuesfrom 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 at7:30 pm! -Adam

03/14/02: Several changes were made to pset #4'sinstructions. Please download the new pdf, the file name ispset4b.pdf -Adam

03/13/02: Please photocopy pset #4 if you want to study for

5.03 Announcements

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

http://www.ilpi.com/organomet/index.html

the exam from your work. The solutions will be posted theafternoon the pset is due, but it will most likely not bereturned 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 thisweek R 3-4 and F 11-12. -Adam

03/05/02: FYI, the avg +/- SD for pset 1, 2, and the examwere:

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 #2have been posted since this afternoon. -Adam

02/26/02: Adam's EXTRA office hours/review session willbe W 2-4 in 8-119. Amrit's extra office hours/review sessionwill be R 4-?, also in 8-119. -Adam

02/26/02: The 3-D molecule files Amrit and I showed inrecitation are online in the notes section. You will have todownload a VRML viewer, and a link to the one I use isincluded. -Adam

02/26/02: Adam will hold extra office hours W 2-4, locationTBA, so check back! Amrit will hold extra office hours R4-?, location TBA. -Adam

02/19/02: Amrit and Adam's office hours are moved to room2-131. Come and see what all the fuss is about Thursday at5. 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 linksto 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 in2-135 instead of 8-205 for this week only.

02/06/02: The syllabus page should be updated with the

5.03 Announcements


correct lecture topics up to P.S. 1's due date. All PS duedates are correct through exam #2 on the calender page (asfar as I know! email me at [email protected] if anything iswrong!) -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


5.03 Announcements



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Spring Term 2002

5.03 Inorganic Chemistry I

This subject deals primarily withchemical bonding and molecularstructure, and their application to thechemistry of representative elements ofthe periodic system. There will be threelectures per week and one recitationsection devoted to discussion of theassigned problems and lecture material.

Lectures: MWF, 10:05AM-10:55AM,Room 2-105

Instructors

Teaching Assistants

Administration:

Kris Grabarek, AssistantDirector of Chem. Education,Room 2-204, x3-0909,[email protected]

Laura Howe, Web Manager,Room 2-204, x8-7492,[email protected]

Jennifer Picray, CourseManager, 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 (onreserve in 14N-132):

Recitations Recitation sections areassigned by the registrar. Changes toassigned recitations will be made in theChemistry Education Office (in persononly, no changes will be made by phoneor e-mail).

5.03 Information

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

Academic Honesty

It is expected that students will maintainthe highest standards of academichonesty.

With respect to homework assignments,it is expected that no student will turn inwork that is not his or her own. Copyingof other students work is not permitted.Full credit will not be awarded foranswers only: remember to show yourwork! Illegible, messy, ordifficult-to-decipher work will not begraded. Copy over your work prior toturning it in if necessary.

It is expected that during a test orexamination, a student will not (1) acceptor use information of any kind from otherstudents; (2) represent the work ofanother student as his or her own; (3) useaids to memory other than thoseexpressly permitted by the examiner.Following a test or examination, astudent will not try to deceive teachers orgraders by misrepresenting or altering hisor her previous work. In advance of a testor exam, a student will not knowinglyobtain access to the exam questions.

Departures from the above standards arecontrary to fundamental principles ofMIT and of the larger scientificcommunity. Such departures areconsidered serious offenses for whichdisciplinary penalties, includingsuspension and expulsion, can beimposed.

5.03 Information




5.03 Information


http://web.mit.edu/



Instructors:

Prof.ChristopherC.Cummins

2-227 [email protected] Hours: 3-4TW in 2-227

Prof.Richard R.Schrock

6-331 x3-1596 [email protected]

Teaching Assistants: Office Hours:

Adam Hock [email protected] R 5-6 2-131

AmritanshuSinha

[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 ofChem. Education, Room 2-204,x3-0909, [email protected]

Laura Howe, Web Manager, Room2-204, x8-7492, [email protected]

Jennifer Picray, Course Manager, Room2-204, x3-7271, [email protected]

5.03 Faculty and Staff

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5.03 Faculty and Staff

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Course CalendarFebruary, 2002

Monday Tuesday Wednesday Thursday Friday

1

4RegistrationDay

5 6Lecture 1SymmetryElementsandOperations

7 8Lecture 2Point GroupAssignments

11Lecture 3CharacterTables

12 13Lecture 4IRSpectroscopyandSymmetry

14 15Lecture 5LGO's andMO's

Problem Set#1 Due inclass

18 President'sDay

19Lecture 6SimpleMO's

PDFMondaySchedule

20Lecture 7BoronHydrideBondingPDF

21 22Lecture 8N and Poxides PDF

25Lecture 9Group 16bondingPDF


26 27Lecture 10Intro toCoordinationChemistryPDF

28

March, 2002


1Lecture 11Exam #1 inclass RoomTBA

5.03 Course Calendar

http://web.mit.edu/5.03/www/calendar.html (1 of 4) [2002-05-14 20:25:17]

4Lecture 12Crystal FieldTheory PDF

5 6Lecture 13Pi-donor/acceptorMO's PDF

7 8Lecture 14ElectronicSpectraPDFAdd Date

11Lecture 15Orgel andTanabe-Suganodiagrams PDF

Problem Set #3Due in class

12 13Lecture 16MagneticProperties ofCoord. compds.PDF

14 15Lecture 17LigandSubsitution:SquarePlanarComplexesPDF

18Lecture LigandSubstitution:OctahedralComplexesPDF

Problem Set #4Due in class

19 20Lecture 19Electron TransferPDF

Exam #2Evening Exam7:30 PM in 2-190

21 22Lecture 20

Cancelleddue to theexam 3/20.

25 SpringBreak Week

26 27 28 29

April, 2002


1Lecture 21Alkyls ofGroups 1, 2,12, 13, and 14PDF

2 3Lecture 22Transitionmetal alkylsand hydridesPDF

4 5Lecture 23ηx-ligandsPDF

8Lecture 24ηx-ligandsand fluxionalprocessesPDF

9 10Lecture 25Metalcarbonylsand clustersPDF


11 12Lecture 26Multiplemetal-ligandandmetal-metalbonds PDF



15 Patriot'sDay Holiday

16Patriot'sDayHoliday

17Lecture 27Reactions ata transitionmetal centerPDF

18 19Lecture 28Homogeneouscatalysis PDF

22Lecture 29Homogeneouscatalysis PDF


23 24Lecture 30

Exam #3 inclass

25Drop Date

26Lecture 31Catalysis PDF

29Lecture 32Catalysis PDF

30

May, 2002


1Lecture 33Metals inBiologyPDF

2 3Lecture 34Metals inBiologyPDF


6Lecture 35Metals inBiologyPDF

7 8Lecture 36Solid StateChemistryPDF

9 10Lecture 37

Solid StateChemistry


13

Lecture 38

LanthanidesandActinides

14 15

Lecture 39

NuclearChemistry

16 17





Problem sets are due in class on the duedate.

ProblemSet Due Solutions

1 PDF 02/15/02 PDF

2 PDF 02/25/02 PDF

3 PDF 03/11/02 PDF

4 PDF* 03/18/02

PDF

fixed pg3

5 PDF 04/10/02 PDF

6 PDF 04/22/02 PDF

7 PDF 05/03/02

8 PDF 05/10/02

* updated!!



5.03 Assignments

http://web.mit.edu/5.03/www/assignments.html [2002-05-14 20:25:18]

http://web.mit.edu/



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 ChemistrySend comments and suggestions to course webmaster: [email protected] updated: April 4, 2002

5.03 Exams

http://web.mit.edu/5.03/www/exams.html [2002-05-14 20:25:19]

http://web.mit.edu/course/5/5.03/www/handouts/exam1key.pdf

http://web.mit.edu/



Getting Textbooks

Textbooks are available at severalbookstores on-line as well as at theCOOP.

Getting Help

Tutoring is available from the TutoringServices Room (TSR) of the Office ofMinority Education. Call TSR at x3-8406any day after 2pm.

Chemistry Sites:

Organometallic Hypertextbook - Thename speaks for itself.

Club Chem - Are you Course 5?Interested in Chemistry? JoinClubChem! Faculty Dinners, ChemistryMagic Shows, etc.

MIT Chemistry Department

WebElements Periodic Table - The firstperiodic table on the WWW. It also has alarge amount of information about eachindividual element such as its history,pictures, compounds, uses, etc.

Character Table (at the bottom!)- Handyif you are ever caught without a copy of achemist's best friend! This is a math site,and presents the theory that culminates incharacter tables.


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

5.03 Resources

http://web.mit.edu/5.03/www/resources.html [2002-05-14 20:25:22]

http://web.mit.edu/tsr/www

http://web.mit.edu/tsr/www

http://web.mit.edu/ome/www/

http://web.mit.edu/ome/www/

http://www.ilpi.com/organomet/index.html

http://web.mit.edu/clubchem/

http://web.mit.edu/chemistry/

http://www.webelements.com/webelements/scholar/index.html

http://mathworld.wolfram.com/CharacterTable.html

http://web.mit.edu/



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 low-spin form, and work through your choice

(iv) determine the total degeneracy of the ground configuration. The formula G!/(N!*(G-N)!), where G is the number of boxes and N the number of equivalent spin ½ particles you can place in those boxes applies. Note: degenerate energy levels may not include all microstates that exist in K symmetry.

(v) Determine the term symbol(s) for the state(s) arising from the ground configuration (tables of direct products will be distributed separately as needed to assist you in this) and confirm that the overall degeneracy matches what you calculated in the previous part. (omit J and M)

(vi) Assign the lowest energy spin-allowed electronic absorption band with reference to the terms involved assuming the strong-field limit. (omit J and M)

(vii) If the complex contains unpaired electrons, calculate the spin-only magnetic moment

A) [Os(CN)6]4-

B) [Ru(NH3)6]2+

C) OsOF5

D) [mer-Re(PMe3)3Cl3]2+

E) [TcO2(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]3-

J) [Fe(OH2)6]2+

K) [Fe(bpy)3]2+

L) [MnO4]2-

M) [Mn(H2O)6]2+

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

Problem set #1 50 Problem set #2 50 Exam #1 in class 100 Problem set #3 50 Problem set #4 50 Exam #2 in evening 150 Total points: 450

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 transition-metal carbonyl complexes. Assign the chromium carbonyl depicted to its proper point group, and determine the number and symmetry types of the CO stretching bands that should be observed in this molecule's infrared spectrum. Below the chromium complex is depicted a rhodium species, and likewise for this species you should determine the number and symmetry types of the carbon monoxide stretching bands in the correct point group for this planar molecule. Determine not only the number of bands expected and their symmetries, but also indicate which of these are expected to be observed in the infrared spectrum. On page 595 of your textbook consult compound labeled (f) in figure 23.10. Assign this molecule to its point group, determine the number and symmetry types of the expected CO stretches for this molecule, and indicate which of these will be infrared active according to the selection rule. Also, for both the chromium and rhodium systems, derive pictures of each of the CO stretching vibrations (labeled with appropriate Mulliken symbols), along with normalized expressions for the symmetry adapted linear combinations. Problem 2 Figure 4.14 on page 100 of your textbook develops the molecular orbital diagram for water. Our first exercise in connection with this diagram will be to construct a table showing how all the valence atomic orbitals of the system are permuted upon carrying out the group operations. This problem takes advantage of the C(2v) point group, so you should consult the relevant character table. Label the hydrogen atoms A and B respectively, and write out the group operations across the top of the table, assuming the water molecule to lie in the yz plane. Then complete the table showing how each of the six valence orbitals of the system are permuted upon carrying out the group operations. Note that since the oxygen atom resides on the intersection of all the symmetry elements, its z axis should be taken to coincide with the molecular C(2) axis. On the other hand, it is common when considering peripheral groups that are symmetry related to direct their local z axes toward the central atom. This is the case for the hydrogens. Note that your book refers to "Ligand group orbitals", whereas I will frequently use the term "Symmetry Adapted Linear Combinations". These terms may be used interchangeably.

Problem 3 You should recognize that the molecular orbital diagrams can be simplified considerably through the application of symmetry concepts. For example, it can be considered that there is for each molecular system a separate molecular orbital diagram for each of the symmetry species, i.e. for each of the Mulliken labels. For this reason, you can divide your analysis of the molecular orbitals of the system up into parts according to the number of symmetry species spanned. Write down the configuration for the ground state of water in terms of the four symmetry species of the C(2v) point group, including both occupied and virtual orbitals. Identify each of the MOs as bonding, nonbonding, or antibonding. Sketch clearly each of the molecular orbitals. Problem 4 On page 256 of your textbook is depicted an alane solvate. Substitute water in place of the THF molecules and derive the MO diagram for this system in the appropriate point group. Present the MO diagram not as a whole but rather as separate MO diagrams for each symmetry species encompassed. Sketch clearly and label each of the MOs. Problem 5 Pentaborane-9 (rocket fuel) is depicted in the center of figure 12.18 of your text on page 272. Label all the atoms and identify the symmetry-related sets. For each of the symmetry-related sets, find the corresponding symmetry-adapted linear combinations (SALCs) of atomic orbitals. Sketch clearly all of the SALCs and write down normalized expressions for them. Write down the most probable configuration for the ground state of pentaborane-9 in terms of the configurations for each of the represented symmetry species. Problem 6 Assume R = H for compound 12.22 (page 268 of your text). Assign the system to a point group, identify symmetry-related sets of valence atomic orbitals, and derive and sketch clearly all the corresponding SALCs. Then write down a probable configuration for the system’s ground state in terms of the represented symmetry species. Problem 7 As in the preceding problem but for N2O4 (see Figure 14.11 on page 335 of your text).

1.

On page 450 of your textbook is given a list of terms introduced in the chapter. Give, in your own words, a complete yet succinct definition for each one of these terms.

2.

Using the methods and concepts introduced in the Monday March 4 lecture, derive the splitting diagrams pictured in figure 20.10 of your textbook, on page 460. Do your derivations differ in any substantial respect with the results pictured in the text? If so, comment on the likely origin of any discrepancies.

3.

A list of terms is provided on page 485 of your textbook. Provided a succinct yet complete definition of each of these terms, using your own words.

4.

On page 486 of your textbook you will find problems 20.2, 20.3, 20.5, 20.8, 20.12, 20.15, 20.18. Solve them.

5.

Consider the Crystal field splitting diagrams for a nickel(II) complex in D(4h) symmetry, with sigma-only donor ligands. Now, recollecting the MO picture in box 20.4 on page 464 of your textbook, consider a nickel(II) complex with a single carbon monoxide ligand included in a square-planar arrangement of ligands. Consider this in C(2v) symmetry, showing which d orbital(s) goes to lower energy vis-a-vis the D(4h) parent complex.

Be sure to label all orbitals in both diagrams with the appropriate symmetry label (Mulliken label).

6.

Find the oxidation state, number of d electrons, and group in the periodic table for the metal in each molecule depicted in figures 19.3, 19.5, 19.6, 19.7, 19.8, 19.9, 19.12, and also in problem 19.11.

7.

Explain in your own words what the relationship is between the figure of figure 20.12 and the corresponding Crystal field view of the same situation.

8.

On page 476 of your textbook you will find self-study exercises 1, 2, and 3. Give corresponding Crystal field splitting diagrams, fully labeled with symmetry labels, and populated with the correct number of electrons in each case.

1

O

O O

O

benzo-12-crown-4

a1g

a2u

e1g

e1u

e2g

a1g

e1g*

e2u

a1g*

e2g*

a2u*

e1u*

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

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.

(e) Explain why W(CH2CH3)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?

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

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

(a) V(η5-C5H5)2 is a violet paramagnetic solid.

(b) Cr(η5-C5H5)2 has two unpaired electrons.

(c) Ni(η5-C5H5)2 has two unpaired electrons.

(d) Co(η5-C5H5)2 can be oxidized readily to {Co(η5-C5H5)2}+.

2

(e) Ni(η5-C5H5)2 can "distort" to a more stable "18 electron" structure that contains another type

of ηx-C5H5 ligand bound to nickel. Draw this structure and rationalize why it is an 18e species.

(f) Although η5-C5H5 compounds are known for main group elements (see chapter 18), η5-C5H5

bonding in p-block elements (e.g., in [Pb(η5-C5H5)2]n is usually relatively weak. Explain in

orbital terms why η5-C5H5 bonding might be weak in the p-block elements versus the transition

metals.

(g) Compounds that contain a η5-C5Me5 ligand are usually much more robust than analogs that

contain a η5-C5H5 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(η5-C5Me5)2 to be a stronger or a weaker reducing agent than Fe(η5-

C5H5)2 and why?

3. (15 pts total; 2.5 each)

(a) In the 100 MHz proton NMR spectrum of Fe(η5-C5H5)(η1-C5H5)(CO)2 at 80°C the

resonances for the η5-C5H5 and the η1-C5H5 ligands are both sharp singlets of area 5. Explain

why the resonance for the η1-C5H5 ligand is a sharp singlet.

(b) Explain in terms of bonding to the metal why a η5-C5R5 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-C5H5 ligand in (a) are found in a

ratio of 2:2:1. Explain why this is the case.

(d) Rh(η5-C5H5)(η2-C2H4)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. At high

Rh

Ho Hi

Ho Hi

Hi Ho

Hi Ho

temperatures only one singlet of area eight is observed for these protons. Explain what is

happening at high temperatures that leads to "equilibration" of the Hi and Ho protons.

(Dissociation of ethylene can be excluded by other experiments.)

3

(e) η3-C3H5 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 4/22/0253 points total

1. (12 points total) Consider two parallel, eclipsed cyclobutadiene rings that ultimately willreceive 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 theHückel 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 constructand 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°.

Co Co

COOC

OC CO

COOC

CO

C

O

A

Co Co

OCOC

OC

CO

COOC

COOC

B

2C3 3C2 2S6

Eu

D3d E i 3σd

A1g 1 1 1 1 1 1

A2g 1 1 -1 1 1 -1

Eg 2 -1 0 2 -1 0

Rz

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

z2

A1u 1 1 1 -1 -1 -1

A2u 1 1 -1 -1 -1 1 z

2 -1 0 -2 1 0 (x,y)

2

(a) (5 pts) Assume that the CO stretches can be isolated from the rest of the atomicdisplacements in the molecule. Using an arrow between each C and O as an indicator of a COstretch, write down the representation for the eight CO stretches (arrows) in molecule B, reduceit to a sum of irreducible representations, and state on that basis how many CO stretches could intheory 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 cansee 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 provethat 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 stretchesare observed experimentally in the region between 1700 and 2000 cm-1. On this basis whichstructure must Co2(CO)8 have?

3. (10 pts total; 2 each)(a) When CO coordinates (weakly) to BH3 its stretching frequency actually increases. Explainwhy. (Note that BH3 is purely a Lewis acid.)(b) Predict whether the highest energy IR absorption in [Mn(CO)6]+ will be higher or lower inenergy than the same absorption in Mo(CO)6, and explain why.(c) Predict whether νCO will be higher or lower in energy in compound A vs. compound B andexplain why.

FeCO

F3PF3P

+Fe

COMe3P

Me3P

+

A B

(d) In (CO)5Cr=C(C6H5)(NMe2), a "Fischer Carbene" complex, the methyl groups on thenitrogen atom are inequivalent on the NMR time scale at low temperature in the proton NMRspectrum. Explain why this is the case.

(e) What is at least one unambiguous piece of evidence that the Ta=C bond in compounds suchas (η5-C5H5)2Ta(CH2)(CH3) or (Me3CCH2)3Ta=CHCMe3 is polarized (+) on Ta and (-) onthe 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.)

CpCp

+

-CpCp

+

- CpCp

+

-

A B C

(a) (2 pts ) Cp2TaH3.

(b) (2 pts ) Cp2WCl2.

(c) (2 pts ) Cp2Ta(CH2)(CH3)

(d) (2 pts ) Cp2Nb(η2-CH2CH2)(C2H5)

(e) (2 pts ) Cp2Zr(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


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

OMe OMe+ C6H5MgBr

Pd(PPh3)4 cat

toluene(a)

(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-2,6-

Me2C6H3)[OCMe(CF3)2]2.

(e) Formation of acetic acid from methanol and CO catalyzed by [Rh(CO)2I2]- and HI; overall

CH3OH + CO → CH3OH.

(f) Hydrogenation of terminal olefins by Rh(PPh3)3Cl at 25°C and 1 atm of H2 in (for example)

benzene.

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

NBD

H

DH

D

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


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 polynorborneneby 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.)

O-t-Bu

Ph

t-Bu

O

OMo

N

t-Bu

i-Pr

i-Pr

Ph

O-t-Bu

Ph+

catalyst

(c) The "Desymmetrization" reaction shown below: (You do not have to explain how the

enantiomer shown arises, just the basic mechanism.)

O

M e M e

Mo

N

Ph

M e

Me

M e M e

O

O

O

Me

HMe

1 mo l % catalyst

no solvent,22 °C , 5 m in

93% ee, 85% y ield

- C 2H4

2

(d) The catalytic oxidation of a hydrocarbon (RH) by the Fe(III) porphyrin species shown below

(a cytochrome monooxygenase).

(porph)NFe

N(porph)

(porph)N N(porph)

S(Cys)

RH + 2 H+ + 2e + O2 H2O + 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.)

CH2CH2OH

NH2

CH3CHOH

NH2

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.

1

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. Pleaseanswer 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 theproblems. You have 90 minutes for this exam; therefore, it is advisable to maximizeyour points by first attempting those questions that are relatively easy and/or carrymore points. Good Luck!

Relevant data are provided on the last two pages.

2

1. Coordination Chemistry – general (20pt)

1.1. What dn configuration is found most commonly for a square planar platinumcomplex? (2pt)

1.2. What dn configuration is found most commonly for an octahedral metal complexof 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 insigma 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+) inspherical 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 havewhat spin multiplicity? (2pt)

3

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 theycorrelated? (3pt)

5. Magnetic Properties (18pt)

1.1. What is the spin-only value of µeff expected for [Cr(NH3)6]Br2 if the complex ishigh-spin? (3pt)

1.2. If it is low-spin? (3pt)1.3. The complex [Co(OH2)6]

2+ exhibits a µeff greater than that predicted by the spin-only formula. Explain the origin of this effect. (5pt)

1.4. A Curie paramagnet exhibits a linear relationship between the temperature andwhat quantity? (2pt)

1.5. Liquid oxygen (which incidentally is blue) is (a) attracted into (b) repelled awayfrom 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 isindicative of an (a) associative or (b) a dissociative pathway? Explain yourchoice. (8pt)

6.2. Chloride opposite chloride is substituted more readily than chloride oppositeammonia, in a square planar complex. What is the name of this effect and whatis its origin in MO terms? (6pt)

6.3. Rates of ligand substitution in octahedral cobalt and chromium systems typicallyare invariant with respect to the nature of the entering ligand, and rather seem todepend mainly on the nature of the leaving group. Of the following mechanisticalternatives, 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 mosttypically encountered in the Y reactant? (2pt)

6.5. Why does a pi-acceptor ligand serve to stabilize the intermediate in substitutionat 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 itfrom an outer-sphere ET process? (2pt)

7.2. Electron transfer is (a) slow (b) fast relative to molecular vibrations of thenuclear 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 ammonialigands. Why is the cobalt complex stable to hydrolysis prior to reduction butunstable afterwards? (5pt)

4

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 He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Character tables:

D4h E2C4

(z)C2 2C'2 2C''2 I 2S4 h

2v

2d

linearfunctions,rotations

quadraticfunctions

cubicfunctions

A1g +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 - x2+y2, z2 -

A2g +1 +1 +1 -1 -1 +1 +1 +1 -1 -1 Rz - -

B1g +1 -1 +1 +1 -1 +1 -1 +1 +1 -1 - x2-y2 -

B2g +1 -1 +1 -1 +1 +1 -1 +1 -1 +1 - xy -

Eg +2 0 -2 0 0 +2 0 -2 0 0 (Rx, Ry) (xz, yz) -

A1u +1 +1 +1 +1 +1 -1 -1 -1 -1 -1 - - -

A2u +1 +1 +1 -1 -1 -1 -1 -1 +1 +1 z - z3, z(x2+y2)

B1u +1 -1 +1 +1 -1 -1 +1 -1 -1 +1 - - xyz

B2u +1 -1 +1 -1 +1 -1 +1 -1 +1 -1 - - z(x2-y2)

Eu +2 0 -2 0 0 -2 0 +2 0 0 (x, y) -(xz2, yz2) (xy2,x2y), (x3, y3)

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 23.2-23.3, 23.7, 23.9

23 Apr 5, F ηx-ligands 23.10-23.11

24 Apr 8, M ηx-ligands and fluxional processes 23.13-23.15

25 Apr 10, W Metal carbonyls and clusters 23.4

Problem set #5 due in class

26 Apr 12, F Multiple metal-ligand and metal-metal bonds 23.12, 22.7

Patriot’s Day Apr 15 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


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


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


38 May 13, M Nuclear Chemistry 2.1-2.6, 2.8

39 May 15, W Lanthanides and Actinides 24.1-24.3, 24.5-24.11

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

inorganic chemistry mit lecture notes

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