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Organometallic Chemistry Introduction

Organometallic Chemistry Introduction. Textbook H: Chapters 1.1 - 1.3.4. Textbook A: Introduction, History, Chapters 1.1 - 1.3. Office hours: after class. Paula Diaconescu TA: Wenliang Huang E-mail: pld@chem.ucla.edu ; huangwenl@ucla.edu. Textbooks. Required texts :

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Organometallic Chemistry Introduction

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  1. Organometallic Chemistry Introduction Textbook H: Chapters 1.1 - 1.3.4 Textbook A: Introduction, History, Chapters 1.1 - 1.3 Office hours: after class Paula Diaconescu TA: Wenliang Huang E-mail: pld@chem.ucla.edu; huangwenl@ucla.edu

  2. Textbooks • Required texts: • Organotransition metal chemistry: From bonding to catalysis by John F. Hartwig, University Science Books, 2010 • Organometallic chemistry and catalysis by Didier Astruc, Springer, 2007 • UCLA subscription: http://www.springerlink.com/content/r36568/ • Recommended: • Organometallics 1: Complexes with Metal-Carbon s Bonds and Organometallics 2: Complexes with Metal-Carbon p Bonds by Manfred Bochmann, Oxford University Press, 1993 (beginner level) • Applied Organometallic Chemistry and Catalysis by Robin Whyman, Oxford University Press, 2003 (beginner level) • Organometallic Chemistry by Gary O. Spessard and Gary L. Miessler, Prentice Hall, Inc., 1997 (intermediate level) • The Organometallic Chemistry of the Transition Metals by Robert H. Crabtree, Wiley Interscience; 2nd edition – 1994 or 3rd edition - 2005 (advanced level) • Homogeneous Catalysis; Understanding the art by Piet W. N. M. van Leeuwen, Kluwer Academic Publishers, 2004 (advanced level) • Article references given during lecture • http://www.ilpi.com/organomet/index.html

  3. Grading • Grading: • Midterm: 30% • Final: 50% • Literature presentation: 20% (10% for content, 5% for answering questions, 5% for asking questions) Bonus (calculated based on the highest grade): 5% for writing a paper on a given topic + 5% for writing an original proposal undergraduates: 5% for attending all seminars listed below all: 5% for asking at least 5 good questions during the seminars listed below • Winter organometallic seminars: • 2/22/2012: ZhaominHou, RIKEN Advanced Science Institute  • 2/29/2012: ParisaMehrkhodavandi, University of British Columbia • 3/7/2012: Davit Zargarian, University of Montreal • 3/14/2012: Malcolm Chisholm, Ohio State University

  4. Administrative details • All lecture notes will be posted before class on http://vohweb.chem.ucla.edu/voh/ • Questions: http://vohweb.chem.ucla.edu/voh/ • Midterm: February 3 (revision on Jan 30 in class) • Literature presentations are on Mondays. First presentation will be on January 23. There will be no classes on Jan 16 and Feb 20 (university holidays). • TA’s discussion section: Tuesday, 1-2 pm, YH 1337 • TA’s office hours: Wednesday, 6-7pm, MSB1210

  5. Frontiers in organometallic chemistry • Definition of organometallic chemistry: transformations of organic compounds using metals. • Organometallic chemistry is at the interface between inorganic and organic chemistry. • Inorganic: subset of coordination chemistry • Organic: subset of synthetic methods • Other interdisciplinary areas • Bioorganometallic chemistry • Surface organometallic chemistry • Fullerene-metal complexes

  6. Energy Consumption, 2009 http://www.eia.doe.gov/oiaf/ieo/highlights.html

  7. Catalysis for Energy • Understand mechanisms and dynamics • Design and control the synthesis of catalyst structures DOE workshop 2007

  8. Catalysis • Environmental : green chemistry, atom efficiency, waste remediation, recycling • Polymeric materials: new polymers and polymer architectures, new monomers, new processes • Pharmaceuticals and fine chemicals: demand for greater chemo-, regio-, stereo-, and enantioselectivity • Feedstocks: practical alternatives to petroleum and natural gas

  9. History: first organometallic compound • 1760 Louis Claude Cadet de Gassicourt (Paris) investigates inks based on cobalt salts and isolates cacodyl from cobalt minerals containing arsenic (CoAs2 and CoAsS2) : As2O3 + 4 CH3COOK  [AsMe2]2 first organometallic compound See editorial:Organometallics2001, 20, 1488 -1498 Timeline: 1751 - Benjamin Franklin: Lightning is electrical 1767: Carbonated water: Joseph Priestley 1778 - Antoine Lavoisier (and Joseph Priestley): discovery of oxygen leading to end of Phlogiston theory

  10. First transition metal organometallic compound • 1827 Zeise’s salt is the first platinum - olefin complex See editorial:Organometallics2001, 20, 2-6 Timeline: 1827: Friction match: John Walker 1827: Fountain-pen : PetrachePoenaru 1827 - Georg Ohm: Ohm's law (Electricity) 1827 - Amedeo Avogadro: Avogadro's law (Gas laws) 1828 - Friedrich Wöhler synthesized urea, destroying vitalism 1829: Steam locomotive: George Stephenson

  11. History: 1900 – 1950 • 1863 Charles Friedel and James Crafts prepare organochlorosilanes • 1890 Ludwig Mond discovers Ni(CO)4 • 1893 Alfred Werner develops the modern ideas of coordination chemistry • 1899 introduction of Grignard reagents • 1912 Nobel prizeVictor Grignard and Paul Sabatier • 1917 Schlenk prepares Li alkyls via transalkylation from R2Hg • 1930 Ziegler and Gilman simplify organolithium preparation, using ether cleavage and alkyl halide metallation, respectively

  12. History: 1950 – 1960 • 1951 – 1952 Discovery of ferrocene, Fe(h5-C5H5)2 • Keally, Pauson, and Miller report the synthesis • Wilkinson and Woodward report the correct structure • 1973 Nobel prizeGeoffrey Wilkinson and Ernst Otto Fischer on sandwich compounds • 1955 Zieglerand Natta develop olefin polymerization at low pressure using mixed metal catalysts (transition metal halide / AlR3)

  13. Ziegler/Natta polymerization • Giulio Natta: Italian chemist, Nobel prize 1963 • Learned of Ziegler’s research, and applied findings to other a-olefins such as propylene and styrene. • Resulting polypropylene was made up of two fractions: amorphous (atactic) and crystalline (tactic).Polypropylene is not produced in radical initiated reactions. Control of polymer tacticity: 1963 Nobel prize for Karl Ziegler and Giulio Natta on Ziegler-Natta catalysts http://www.nobel.se/chemistry/laureates/1963/

  14. History: 1960 – 1980: catalysis • 1962: Vaska’s complex • 1964: Fischer reports the first metal carbene.

  15. History: olefin metathesis • 1964: Banks reports the first example of olefin metathesis. • 1971: Yves Chauvin proposes mechanism. • 1974: Schrock synthesizes first metal alkylidene complex.

  16. 2005 Nobel prize in chemistry

  17. 2010 Nobel prize in chemistry Akira Suzuki

  18. 2010 Nobel prize in chemistry Richard F. Heck Ei-ichi Negishi

  19. Ligands in organometallic chemistry • Neutral 2e donors: PR3 (phosphines), CO (carbonyl), R2C=CR2 (alkenes), RC≡CR (alkynes, can also donate 4e), N≡CR (nitriles) • Anionic 2e donors: X- (halide), CH3- (methyl), CR3- (alkyl), Ph- (phenyl), H- (hydride) The following can also donate 4e if needed, but initially count them as 2e donors (unless they are acting as bridging ligands): OR- (alkoxide), SR- (thiolate), NR2- (inorganic amide), PR2- (phosphide) • Anionic 4e donors: C3H5- (allyl), O2- (oxide), S2- (sulfide), NR2- (imide), CR22- (alkylidene)and from the previous list: OR- (alkoxide), SR- (thiolate), NR2- (inorganic amide), PR2- (phosphide) • Anionic 6e donors: Cp- (cyclopentadienyl), O2- (oxide) • Z ligands: do not bring e to the metal: BR3, AlR3

  20. Nomenclature h1-dppe / k1-dppe - bridging ligand

  21. Ordering: from ACS publications • In formulas with Cp (cyclopentadienyl) ligands, the Cp usually comes first, followed by the metal center: Cp2TiCl2 • Other anionic multi-electron donating ligands are also often listed in front of the metal. • In formulas with hydride ligands, the hydride is sometimes listed first. • Rule # 1, however, takes precedence over this rule: HRh(CO)(PPh3)2 and Cp2TiH2 • Bridging ligands are usually placed next to the metals in question, then followed by the other ligands • Note that rules 1 & 2 take precedence: Co2(m-CO)2(CO)6, Rh2(m-Cl)2(CO)4, Cp2Fe2(m-CO)2(CO)2

  22. Coordination geometries

  23. Coordination geometries

  24. Coordination geometries

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