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Abstract/Syllabus:
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Cummins, Christopher, 5.05 Principles of Inorganic Chemistry III, Spring 2005. (Massachusetts Institute of Technology: MIT OpenCourseWare), http://ocw.mit.edu (Accessed 09 Jul, 2010). License: Creative Commons BY-NC-SA
Spring 2005
Illustration of phosphinocarbene. (Figure by Prof. Christopher Cummins.)
Course Highlights
This course features a selection of downloadable lecture notes.
Course Description
This course covers the principles of main group (s and p block) element chemistry with an emphasis on synthesis, structure, bonding, and reaction mechanisms.
Syllabus
Recommended Textbooks
The following texts are strongly recommended as they provide a helpful background for the topics covered in class:
Greenwood, Norman, and A. Earnshaw. Chemistry of Elements. Oxford, UK: Elsevier Science, 1997. ISBN: 9780750633659.
Bader, Richard F. Atoms in Molecules: A Quantum Theory. Oxford, UK: Oxford University Press, Inc., 1994. ISBN: 9780198558651.
Class Work and Exams
In addition to lecture topics, problems will be presented to students in class for group problem solving sessions. There are no formal homework assignments. For Exam 2, students are required to give an oral presentation worth 20% of their grade. There are two additional exams - one is an in-class exam, and the other is in take-home format.
Grading
Grading Table
| ACTIVITIES |
PERCENTAGES |
| Exam 1 (In-class) |
20% |
| Exam 2 (Oral Presentation) |
20% |
| Exam 3 (Take-home) |
20% |
| Class Participation (Discussion, Questions, Problem Solving) |
40% |
Calendar
Calendar Table
| LEC # |
TOPICS |
| 1 |
Introduction and Theory |
| 2 |
Aluminum Chemistry I |
| 3 |
Aluminum II |
| 4 |
Phosphorus |
| |
Exam 1 (In-class) |
| 5 |
Gallium and Indium |
| 6 |
Gallium Multiple Bonds |
| 7 |
Gallium, Phosphorus, and Tin |
| |
Exam 2 (Oral Presentations) |
| 8 |
Nitrogen, Halogens, Noble Gases |
| 9 |
Fluorine, Krypton |
| 10 |
Relativistic Effects |
| 11 |
Gold, Fluorine, Xenon |
| |
Exam 3 (Take-home) |
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Further Reading:
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Readings
Readings Table
| LEC # |
TOPICS |
READINGS |
| 1 |
Introduction and Theory |
Molina, J., and J. A. Dobado. "The three-center-four-electron (3c-4e) bond nature revisited. An atoms-in-molecules theory (AIM) and ELF study." Theoretical Chemistry Accounts 105 (2001): 328-337.
Dobado, J. A., H. Martinez-Garcia, and J. M. Molina, et. al. "Chemical Bonding in Hypervalent Molecules Revised. Application of the Atoms in Molecules Theory to Y3X and Y3XZ (Y = H or CH3; X = N, P or As; Z = O or S) Compounds." J Am Chem Soc 120 (1998): 8461-8471.
Dobado, J. A., H. Martinez-Garcia, and J. M. Molina, et. al. "Chemical Bonding in Hypervalent Molecules Revised. 2. Application of the Atoms in Molecules Theory to Y2XZ and Y2XZ2 (Y = H, F, CH3; X = O, S, Se; Z = O, S) Compounds." J Am Chem Soc 121 (1999): 3156-3164.
Dobado, J. A., H. Martinez-Garcia, and J. M. Molina, et. al. "Chemical Bonding in Hypervalent Molecules Revised. 3. Application of the Atoms in Molecules Theory to Y3X-CH2 (X = N, P, or As ; Y = H or F) and H2X-CH2 (X = O, S, or Se) ylides." J Am Chem Soc 122 (2000): 1144-1149.
Obituary: José Molina Molina in memoriam. Theor Chem Acc 105 (March 21, 2001): 270.
Dobado, J. A., H. Martinez-Garcia, and J. M. Molina, et. al. "Theoretical Bonding Description of Alkylidene Chalcogen (O, S, Se) Difluorides (H2C=XF2): Planar versus Bent Conformations." Inorg Chem 38 (1999): 6257-6260.
Molina, J., J. A. Dobado, G. L. Heard, R. F. W. Bader, and M. R. Sundberg. "Recognizing A Triple Bond Between Main Group Atoms." Theoretical Chemistry Accounts 105 (2001): 365-373. |
| 2 |
Aluminum Chemistry I |
Hardman, Ned J., Chunming Cui, Herbert W. Roesky, William H. Fink, and Philip P. Power. "Stable, Monomeric Imides of Aluminum and Gallium: Synthesis and Characterization of [{HC(MeCDippN)2}MN-2,6-Trip2C6H3] (M=Al or Ga; Dipp=2,6-iPr2C6H3; Trip=2,4,6-iPr3C6H2)." Angewandte Chemie International Edition 40, no. 11 (June 1, 2001): 2172-2174.
Cui, Chunming, Herbert W. Roesky, Hans-Georg Schmidt, and Mathias Noltemeyer. "[HC{(CMe)(NAr)}2]Al[(NSiMe3)2N2] (Ar=2,6-iPr2C6H3): The First Five-Membered AlN4 Ring System." Angewandte Chemie International Edition 39, no. 24 (December 15, 2000): 4531-4533.
Peng, Ying, Hongjun Fan, Hongping Zhu, Herbert W. Roesky, Jörg Magull, and Colan E. Hughes. "[{HC(CMeNAr)2}2Al2P4] (Ar=2,6-iPr2C6H3): A Reduction to a Formal {P4}4- Charged Species." Angewandte Chemie International Edition 43, no. 26 (June 28, 2004): 3443-3445.
Cui, Chunming, Herbert W. Roesky, Hans-Georg Schmidt, Mathias Noltemeyer, Haijun Hao, and Fanica Cimpoesu. "Synthesis and Structure of a Monomeric Aluminum(i) Compound [{HC(CMeNAr)2}Al] (Ar=2,6-iPr2C6H3): A Stable Aluminum Analogue of a Carbene." Angewandte Chemie 39, no. 23 (December 1, 2000): 4274-4276.
Neculai, Dante, Herbert W. Roesky, Ana Mirela Neculai, Jörg Magull, Bernhard Walfort, and Dietmar Stalke. "Formation and Characterization of the First Monoalumoxane, LAlO-B(C6F5)3." Angewandte Chemie International Edition 41, no. 22 (November 15, 2002): 4294-4296.
Arduengo, Anthony J., III David A. Dixon, Kristin K. Kumashiro, Chengteh Lee, William P. Power, and Kurt W. Zilm. "Chemical Shielding Tensor of a Carbene." J Am Chem Soc 116, no. 14 (1994): 6361-6367.
Cui, C., S. Kopke, R. Herbst-Irmer, H. W. Roesky, M. Noltemeyer, H.-G. Schmidt, and B. Wrackmeyer. "Facile Synthesis of Cyclopropene Analogues of Aluminum and an Aluminum Pinacolate, and the Reactivity of LAl[η2-C2(SiMe3)2] toward Unsaturated Molecules (L = HC[(CMe)(NAr)]2, Ar = 2,6-i-Pr2C6H3)." J Am Chem Soc (Article) 123, no. 37 (2001): 9091-9098. |
| 3 |
Aluminum II |
Purath, Andreas, Carsten Dohmeier, Achim Ecker, Hansgeorg Schnöckel, Kerstin Amelunxen, Thomas Passler, and Nils Wiberg." Synthesis and Crystal Structure of the Tetraaluminatetrahedrane Al4[Si(t-Bu)3]4, the Second Al4R4 Compound." Organometallics 17 (1998): 1894-1896.
Purath, Andreas, Carsten Dohmeier, Achim Ecker, Ralf Koppe, Harald Krautscheid, Hansgeorg Schnöckel, Reinhart Ahlrichs, Carsten Stoermer, Jochen Friedrich, and, Peter Jutzi. "Synthesis and Structure of a Neutral SiAl14 Cluster." J Am Chem Soc 122 (2000): 6955-6959.
Schnöckel, Hansgeorg, and Harald Köhnlein. "Synthesis and Structure of Metalloid Aluminum Clusters - Intermediates on the Way to the Elements." Polyhedron 21 (2002): 489-501. |
| 4 |
Phosphorus |
Shah, Shashin, M. Cather Simpson, Rhett C. Smith, and John D. Protasiewicz. "Three Different Fates for Phosphinidenes Generated by Photocleavage of Phospha-Wittig Reagents ArP=PMe3." J Am Chem Soc 123 (2001): 6925-6926.
Rhett C. Smith, Shashin Shah, Eugenijus Urnezius, and John D. Protasiewicz. "An Unusual Equilibrium Chlorine Atom Transfer Process and Its Potential for Assessment of Steric Pressure by Bulky Aryls." J Am Chem Soc 125 (2003): 40-41.
Smith, Rhett C., Peter Gantzel, Arnold L. Rheingold, and John D. Protasiewicz. "Arsa-Wittig Complexes (ArAs=PMe3) as Intermediates to Diarsenes." Organometallics 23 (2004): 5124-5126.
Smith, Rhett C., Tong Ren, and John D. Protasiewicz. "A Robust, Reactive, and Remarkably Simple to Prepare Sterically Encumbered meta-Terphenyl Ligand." Eur J Inorg Chem (2002): 2779-2783.
Macikenas, D., E. Skrzypczak-Jankun, and J. D. Protasiewicz. "A New Class of Iodonium Ylides Engineered as Soluble Primary Oxo and Nitrene Sources." J Am Chem Soc (Communication) 121, no. 30 (1999): 7164-7165.
Shah, Shashin, John D. Protasiewicz. "'Phospha-variations' on the themes of Staudinger and Wittig: phosphorus analogs of Wittig reagents." Coordination Chemistry Reviews 210 (2000): 181-201.
Smith, Rhett C., and John D. Protasiewicz. "Conjugated Polymers Featuring Heavier Main Group Element Multiple Bonds: A Diphosphene-PPV." J Am Chem Soc 126 (2004): 2268-2269.
Chen, Xufang, Rhett C. Smith, and John D. Protasiewicz. "Cycloaddition of phosphanylidene-σ4-phosphoranes ArP=PMe3 and quinones to yield 1,3,2-dioxophospholanes." Chem Commun (2004): 146-147.
Macikenas, Dainius, Ewa Skrzypczak-Jankun, and John D. Protasiewicz. "Redirecting Secondary Bonds To Control Molecular and Crystal Properties of an Iodosyl- and an Iodylbenzene." Angewandte Chemie International Edition 39, no. 11 (June 2, 2000): 2007-2010.
Shah, Shashin, Tom Concolino, Arnold L. Rheingold, and John D. Protasiewicz. "Sterically Encumbered Systems for Two Low-Coordinate Phosphorus Centers." Inorg Chem 39 (2000): 3860-3867.
Dutan, Cosmina, Shashin Shah, Rhett C. Smith, Sylvie Choua, Theó Berclaz, Michel Geoffroy, and John D. Protasiewicz. "Sterically Encumbered Diphosphaalkenes and a Bis(diphosphene) as Potential Multiredox-Active Molecular Switches: EPR and DFT Investigations." Inorg Chem 42 (2003): 6241-6251.
Smith, Rhett C., and John D. Protasiewicz. "A Trans-Spanning Diphosphine Ligand Based on a m-Terphenyl Scaffold and Its Palladium and Nickel Complexes." Organometallics 23 (2004): 4215-4222.
Shah, Shashin, Glenn P. A. Yap b, and John D. Protasiewicz. "Crystal structure of the phosphanylidene-σ4-phosphorane DmpP=PMe3 (Dmp=2,6-Mes2C6H3) and reactions with electrophiles." Journal of Organometallic Chemistry 608 (2000): 12-20. |
| 5 |
Gallium and Indium |
Uhl, Werner, Lars Cuypers, Rene Graupner, Jens Molter, Annegret Vester, and Bernhard Neumüller. "Einfache Synthese von Alkylaluminium- und Alkylgalliumhydriden - Kristallstrukturen von [(Me3C)2GaH]3 und den neuartigen Sesquihydriden [(Me3C)2EH]2[EH2CMe3]2 (E = Al, Ga)." Zeitschrift für anorganische und allgemeine Chemie 627, no. 4, (April, 2001): 607-614.
Uhl, Werner, Lars Cuypers, Bernhard Neumüller, and Frank Weller. "Hydrogallation of Alkynes: Syntheses of Carbon-Gallium Cages Possessing Heteroadamantane Structures." Organometallics 21 (2002): 2365-2368.
Uhl, Werner, Maike Benter, and Malte Prött. "Replacement of CO ligands by the isolobal gallium(I) compound GaR [R = C(SiMe3)3], formation of the transition metal gallium compounds Mn2(CO)8 2 and Fe3(CO)9(μ-CO)(μ-GaR)2." J Chem Soc, Dalton Trans (2000): 643-646.
Uhl, Werner, Sandra Melle, Gernot Frenking, and Michael Hartmann. "Reaction of Ni2Cp2(μ-CO)2 with the Alkylgallium(I) and Alkylindium(I) Compounds E4[C(SiMe3)3]4 (E = Ga, In). Insertion of E-R Groups into the Ni-Ni Bond versus Replacement of CO by the Isolobal E-R Ligands." Inorg Chem 40 (2001): 750-755.
Uhl, Werner, Lars Cuypers, Malte Prött, and Klaus Harms. "Molecular Self-assembly Controlled by gallium-gallium single bonds-facile Syntheses of Macrocyclic Octagallium Compounds." Polyhedron 21 (2002): 511-518.
Uhl, Werner, Lars Cuypers, Klaus Harms, Wolfgang Kaim, Matthias Wanner, Rainer Winter, Rainer Koch, and Wolfgang Saak. "Ga9(CMe3)9, an Important New Building Block in the Structural Chemistry of the Alkylelement(I) Compounds EnRn (E=B-In)." Angewandte Chemie International Edition 40, no. 3 (February 2, 2001): 566-568.
Uhl, Werner, and Maike Benter. "Formation of a gallium triphosphorus heterocycle by reaction of the alkylgallium(I) compound Ga4[C(SiMe3)3]4 with tri(tert-butyl) cyclotriphosphane." J Chem Soc, Dalton Trans (2000): 3133-3135.
Uhl, Werner, Sandra Melle, Gertraud Geiseler, and Klaus Harms. "In3I2[C(SiMe3)3]3: Synthesis of a Diiodotrialkyltriindane(5) Containing Two In-In Single Bonds." Organometallics 20 (2001): 3355-3357.
Uhl, Werner, Fritjof Schmock, und Gertraud Geiseler. "[In3Br3{C(SiMe3)3}3][Li(THF)3] mit einer Kette aus drei Indiumatomen ein bemerkenswertes Nebenprodukt aus der Synthese des Tetraindiumclusters In4[C(SiMe3)3]4." Z Anorg Allg Chem 628 (2002): 1963-1966.
Uhl, Werner, and Sandra Melle. "Alkylindium Subhalides Derived from the Tetrahedral Indium(i) Cluster Compound [In4{C(SiMe3)3}4]." Chem. Eur. J. 7, no. 19 (2001).
Uhl, Werner, Jens Molter, and Bernhard Neumuller. "Dialkylaluminum Hydrazides Derived from Free Hydrazine N2H4. Molecular Structures of [(Me3C)2AlN2H3]2 and [(Me3C)2Al]4(N2H2)2." Inorg Chem 40 (2001): 2011-2014.
Uhl, Werner, und Sandra Melle. "Pt[In-C(SiMe3)3]4 - a Pt(CO)4 Analogous Compound with a Platinum Atom Tetrahedrally coordinated by Four InR Ligands." Z Anorg Allg Chem 626 (2000): 2043-2045.
Uhl, Werner, Lars Cuypers, Klaus Harms, Wolfgang Kaim, Matthias Wanner, Rainer Winter, Rainer Koch, and Wolfgang Saak. "Ga9(CMe3)9, an Important New Building Block in the Structural Chemistry of the Alkylelement(I) Compounds EnRn (E=B-In)." Angewandte Chemie International Edition 40, no. 3 (February 2, 2001): 566-568.
Uhl, Werner, Frank Breher, and Bernhard Neumüller. "Reactions of Carbaalanes with HBF4 and HCl: A μ3-Bridging Fluorine Atom in (AlEt)7(C=CHPh)2(CCH2Ph)3(μ3-F) versus a Terminal Chlorine Atom in (AlMe)7(AlCl)(CCH2Ph)5H." Organometallics 20 (2001): 5478-5484.
Uhl, Werner, Frank Breher, Alphonse Mbonimana, Jürgen Gauss, Detlev Haase, Arne Lützen, and Wolfgang Saak. "New Carbaalanes - (AlMe)8(CCH2Me)5(C≡C-Me) and the THF Adduct (AlMe)8(CCH2Me)5H·2THF." Eur J Inorg Chem 2001: 3059-3066.
Uhl, Werner, Maike Benter, Sandra Melle, Wolfgang Saak Gernot Frenking, and Jamal Uddin. "Synthesis and Structure of [Ni{Ga-C(SiMe3)3}4] and Quantum-Chemical Verification of Strong π Back-Bonding in the Model Compounds [Ni(EMe)4] (E = B, Al, Ga, In, Tl)." Organometallics 18 (1999): 3778-3780. |
| 6 |
Gallium Multiple Bonds |
Su, Jianrui, Xiao-Wang Li, and Gregory H. Robinson. "2,6-Bis(2,4,6-triisopropylphenyl)phenyl as an extraordinarily bulky ligand in organometallic chemistry. Synthesis and molecular structure of (Mes*2C6H3)MCl2]2 (M = Ga, In; Mes* = C6H2Pri3-2,4,6)." Chem Commun (1998): 2015-2016.
Robinson, Gregory H. "Gallanes, Gallenes, Cyclogallenes, and Gallynes: Organometallic Chemistry about the Gallium-Gallium Bond." Acc Chem Res 32 (1999): 773-782.
Xie, Y., P. R. Schreiner, H. F. Schaefer, III, X. -W. Li, and G. H. Robinson. "Are Cyclogallenes [M2(GaH)3] (M = Li, Na, K) Aromatic?" J Am Chem Soc (Article) 118, no. 43 (1996): 10635-10639.
Su, J., X. -W. Li, R. C. Crittendon, C. F. Campana, and G. H. Robinson. "Experimental Confirmation of an Iron-Gallium Multiple Bond: Synthesis, Structure, and Bonding of a Ferrogallyne." Organometallics (Communication) 16, no. 21 (1997): 4511-4513.
Su, J., X. -W. Li, R. C. Crittendon, and G. H. Robinson. "How Short is a -Ga≡Ga- Triple Bond? Synthesis and Molecular Structure of Na2[Mes*2C6H3-Ga≡Ga-C6H3Mes*2] (Mes* = 2,4,6-i-Pr3C6H2): The First Gallyne." J Am Chem Soc (Communication) 119, no. 23 (1997): 5471-5472.
Robinson, Gregory H. "On the Organometallic Chemistry of Gallium and the Dynamics of Ga-Ga Bond Formation." Chem Commun (2000): 2175-2181.
Grutzmacher, H, and TF Fassler. "Topographical Analyses of Homonuclear Multiple Bonds between Main Group Elements." Chemistry 6, no. 13 (Jul 3, 2000): 2317-25.
Xie, Y., R. S. Grev, J. Gu, H. F. Schaefer, III, P. v. R. Schleyer, J. Su, X. -W. Li, and G. H. Robinson. "The Nature of the Gallium-Gallium Triple Bond." J Am Chem Soc (Article) 120, no. 15 (1998): 3773-3780. |
| 7 |
Gallium, Phosphorus, and Tin |
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| 8 |
Nitrogen, Halogens, Noble Gases |
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| 9 |
Fluorine, Krypton |
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| 10 |
Relativistic Effects |
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| 11 |
Gold, Fluorine, Xenon |
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