Chem 622: Organometallic Chemistry Class: MWF, 1030 – 1120 AM, Bilger 341C Instructor: Matt Cain Textbook(s): Crabtree, 6 th Edition, The Organometallic Chemistry of the Transition Metals AND Elschenbroich, 3 rd Edition, Organometallics Organometallic Chemistry bridges the imaginary gap between organic and inorganic chemistry. Despite being a rather new field (Ferrocene 1951), its utility and practicality are undeniable. The production of L-DOPA, S-Metolachlor, and (–)- Menthol are just some of the commodities produced on a colossal scale due to the employment of organometallics catalysts. This class will focus on the entire Periodic Table of Elements and will introduce the fundamental trends in both the Main Group and Transition Metals. Students should gain an understanding of these fundamentals and be able to apply them to published research, with the ultimate goal of applying it to their own! In addition, some topics/complexes will be evaluated from a historical prospective, in which they first appeared as structural anomalies and have evolved (through synthesis, etc.) to become highly useful ligands, intermediates, or catalysts. A common theme throughout the class will be to connect the material from the classroom to relevant and published research, with the hope that students will recognize that although many fields of chemistry (organic, inorganic, physical, supramolecular, etc.) are taught separately, they are interdisciplinary and often times, directly linked by organometallic chemistry. Fe Fe PPh 2 PPh 2 Fe PR 2 PR' 2 dppf Josiphos N O Cl H 3 CO S-Metolachlor Ferrocene R Li Li Li R R R Li Li Li Li Li R Structure and Bonding P R 1 R 2 R 3 R 1 S R 2 O Chiral Molecules NMR Spectroscopy Reactivity ZnEt 2 in air History, Development, Evolution, and Application Main Group Organometallics and Catalysis N N H H Main Group Applications 31 P NMR 19 F NMR 6 Li NMR 7 Li NMR Olefin Metathesis R M R M R R + R M R Asymmetric Hydrogenation OEt O O OEt OH O M C O Ligands and Bonding CO: σ-donor / π-acceptor DCD Model M O C M C C Isolobal Analogy d 7 –ML 5 CH 3 (CO) 5 Mn CH 3 (CO) 5 Mn Mn(CO) 5 H 3 C CH 3 M RX M X R M R' R R'-M' M'-X RR' Cross Couplings M P P H/D FG Symmetry and Chirality Kinetic Isotope Effects Electron Counting Pt P P Ph Cl Cp Ta Cp CH 2 CH 3
Elschenbroich,3rdEdition,OrganometallicsOrganometallicChemistrybridgestheimaginarygapbetweenorganicandinorganicchemistry. Despite being a rather new field (Ferrocene 1951), its utility andpracticality are undeniable. The production of L-DOPA, S-Metolachlor, and (–)-Mentholare justsomeof thecommoditiesproducedonacolossalscaleduetotheemployment of organometallics catalysts. This class will focus on the entirePeriodicTableofElements andwill introduce the fundamental trends inboth theMainGroupandTransitionMetals.Studentsshouldgainanunderstandingofthesefundamentals and be able to apply them to published research,with the ultimategoal of applying it to their own! In addition, some topics/complexes will beevaluated fromahistoricalprospective, inwhich they first appearedas structuralanomalies and have evolved (through synthesis, etc.) to become highly usefulligands, intermediates,orcatalysts. Acommonthemethroughouttheclasswillbetoconnectthematerialfromtheclassroomtorelevantandpublishedresearch,withthe hope that students will recognize that although many fields of chemistry(organic, inorganic, physical, supramolecular, etc.) are taught separately, they areinterdisciplinaryandoftentimes,directlylinkedbyorganometallicchemistry.
Fe FePPh2
PPh2Fe
PR2
PR'2
dppf Josiphos
N
OCl
H3CO
S-MetolachlorFerrocene
R
LiLi
Li
RR
R
Li
LiLiLi
Li R
Structure and Bonding
PR1 R2
R3R1
SR2
O
Chiral MoleculesNMR Spectroscopy
Reactivity
ZnEt2 in air
History, Development, Evolution, and Application Main Group
- Landmark compounds and reactions, Evolution ofInorganic/OrganometallicChemistry,NobelPrizeWinners
MainGroup
- StructureandBondingofGroups1,2,13–16- SynthesisofMainGroupCompounds- DOSYNMRspectroscopy- ReactivityandhandlingofMainGroupCompounds- Trends in bond strength/length, polarity of M-C bond,
- Tour of the ligands: σ-donors, σ-donors/π-acceptor, π-donors,commonligands(CO,PR3,halides,etc.),backbondingand its effect (IR spectroscopy, quantification of electrondensity)
- Isolobal Analogy and its Application: understanding andpredictingbonding,RoaldHoffman(1981NobelPrize)
- Reactions at the Metal: Ligand Dissociation/Association,OxidativeAddition/ReductiveElimination,and the impactofstericsandelectronics
- Reactions involving the Ligands: Insertion/β-hydrideelimination, nucleophilic/electrophilic attack, and how topromote or inhibit these processes. Examination of Bredt’sRule,agosticinteractions,etc.
