6/11/2015Hot Topics and Hypes1 Hot Topics en Hypes in organometallic chemistry.

Slides:

Advertisements

Similar presentations

Organometallic Chemistry an overview of structures and reactions

Advertisements

Reactions and Reaction Mechanisms A reaction mechanism shows the actual flow of electrons and movement of the atoms during the reaction. If one can understand.

Chemsheets AS006 (Electron arrangement)

Electrophilic Addition to Alkenes. Addition of H-X to the Carbon- Carbon Double Bond: Markovnikov’s Rule In its original form, Markovnikov’s rule states.

Oxidative Addition/Reductive Elimination

Main-group Organometallics Peter H.M. Budzelaar. Main-Group Organometallics 2 Main group organometallics at a glance Structures –  bonds and 3c-2e (or.

Section 20.1 Saturated Hydrocarbons 1.To understand the types of bonds formed by the carbon atom 2.To learn about the alkanes 3.To learn about structural.

Catalytic Reaction Kinetics

General Principles Definition of a Catalyst Energetics of Catalysis Reaction Coordinate Diagrams of Catalytic Reactions.

Alcohols: Structure & Synthesis

Transition-metal Organometallics

Lecture 37 Organometallic reactions and catalysis 1) Catalytic olefin hydrogenation A thermodynamically favorable reaction may be slow at modest temperatures.

Created by Athena Anderson, Brette Chapin, Michelle Hansen and Kanny Wan and posted on VIPEr June Copyright Brette Chapin This work is licensed.

6/1/2015Carbenes en Olefin Metathesis1 Carbenes en carbynes alkene en alkyne metathesis Schrock en Fischer carbene complexes Stable carbenes Cyclopropanation,

Ligand Substitution Reactivity of Coordinated Ligands Peter H.M. Budzelaar.

Oxidative Addition and Reductive Elimination Peter H.M. Budzelaar.

Insertion and elimination olefin polymerization

Carbenes and Olefin Metathesis Peter H.M. Budzelaar.

Dissociative Associative

1 CH402 Asymmetric catalytic reactions Prof M. Wills Think about chiral centres. How would you make these products? Think about how you would make them.

Organometallic Chemistry between organic and inorganic Peter H.M. Budzelaar.

Organometallic Chemistry an overview of structures and reactions Peter H.M. Budzelaar.

What makes the carbonyl carbon electrophilic? 1.RESONANCE: What would the resonance hybrid look like? 2.INDUCTION: The carbonyl carbon is bonded to a very.

ChE 553 Lecture 23 Catalysis By Surfaces 1. Objective For Today Ask How Surfaces Can Catalyze Reactions 2.

What is Inorganic Chemistry?. What is Organic Chemistry? I found all texts arranged like this: Structure and bonding Acids and bases Alkanes- reactions.

ORGANIC CHEMISTRY AS CHEM. STUDY GUIDE. DEFINE FREE RADICALS Atoms (or groups of atoms) with unpaired electrons.

The d-block Coordination Chemistry. Objectives Must Explain and use the terms ligand/complex/complex ion and ligand substitutions. Should Describe the.

Catalyst design driven by fundamental research How do we extrapolate from molecular (picoscale) and nanoscale fundamentals to operating catalytic systems?

ORGANIC CHEMISTRY. Uniqueness of carbon Can form multiples bonds to itself and with other atoms of other elements The strength of the C-C and C-H bond.

Application of Organometallic Chemistry – Breaking the Inert C-H Bond

I. Organometallic Reagents = carbon-metal bonds

1 Chapter 13 Silicon reagents  General features  Two other highly important properties of silicon  Reactions of organosilanes  1,2 rearrangements (Brook.

CH 20: Carboxylic Acids and Nitriles Renee Y. Becker CHM 2211 Valencia Community College 1.

Introduction to catalysis Textbook H: Chapter 14 Textbook A: Part IV – Introduction.

Enzymes (Ch. 6) Intro Basics of catalysis General types of catalysis Quantification of catalysis –enzyme kinetics and inhibition Specific examples Allostery.

127 Chapter 6: Reactions of Alkenes: Addition Reactions 6.1: Hydrogenation of Alkenes – addition of H-H (H 2 ) to the π-bond of alkenes to afford an alkane.

Hydroformylation and oxidation of olefins Textbook H: Chapter 16.6, 17.1 – 17.3 Textbook A: Chapter 16.1 – 16.2, 18.1 – 18.2.

Conjugated dienes, aromaticity. Allylic and benzylic reactivity. Phenols.

18 electron rule: EAN rule (Effective Atomic Number)

Hemiacetal and Acetal Functional Groups Hemiacetal: alcohol and ether on same carbon Acetal: Two ethers on same carbon.

CHEMISTRY 4000 Topic #2: Functional Group Oriented Bond-Sets Fall 2012 Dr. Susan Findlay.

CHEMISTRY 2600 Topic #3: Electrophilic Addition Reactions of Alkenes and Alkynes Spring 2008 Dr. Susan Lait.

Chemistry 1011 Slot 51 Chemistry 1011 TOPIC Acids and Bases TEXT REFERENCE Masterton and Hurley Chapter 4.2 (Review), 13, 14.1, 15.1 (page 427), 21.2 (page589)

Chiral Synthesis Jointly done by: Lin Wan Shi, Serene Loo, Sadia Riaz, Eran Sim, G. Girish from Temasek Junior College, Singapore.

9.7 Catalytic Hydrogenation The addition of H 2 across a C=C double bond If a chirality center is formed, syn addition is observed Draw the stereoisomers.

16 Reactions of inorganic compounds in aqueous solution 16.1 Lewis acids and bases 16.2 Ligand substitution reactions 16.3 Summary: Acid-Base and substitution.

Colors and Spectroscopy of Transition Metal Complexes.

Tandem carbonylation reaction. Monsanto Process (Acetic acid Synthesis): o c, 1-40 atm Ref: BASF process: cobalt-based high pressure process.

TRANSITION METAL COMPLEXES.

Efficiency in Synthesis

Colors and Spectroscopy of Transition Metal Complexes

Heterogeneous Cu Catalysts in C-N & C-O Coupling Reactions

Discovery of Molecular Oxidation Catalysts Using Metallo-Enzyme Mimicry and Combinatorial Chemistry Stephen B. Colbran & D. Brynn Hibbert, School of Chemistry,

Ligand substitution reactions: dissociative

CH 12-3: Grignard Reaction-I

Standard Organometallic Reaction Types

Introduction Main Group Metals

High Oxidation State, Late Transition Metals Featuring Metal-Ligand Multiple Bonds: Strategies for Sequential C-H Bond Activation and Functionalization.

Organometallic Chemistry

GRIGNARDS REAGENT NEW CHAPTER R-Mg-X.

GRIGNARDS REAGENT NEW CHAPTER R-Mg-X.

Colors and Spectroscopy of Transition Metal Complexes

REACTIONS OF GRIGNARD REAGENTS

in organometallic chemistry

GRIGNARD’S REAGENT R-Mg-X.

Introduction Transition Metals

Organometallic Chemistry

Confirmation of the Improbable

Presentation transcript:

6/11/2015Hot Topics and Hypes1 Hot Topics en Hypes in organometallic chemistry

6/11/2015Hot Topics and Hypes2 Hot Topics Ideal conversions with (nearly) incompatible requirements: C-H activation and other "all-in-one" conversions Selective oxidations Anti-Markovnikov water addition (Co)polymerization of functionalized olefins Chiral conversions Mechanisms / models of enzymes

6/11/2015Hot Topics and Hypes3 Hypes Everything "BIO" and "NANO" Buckyballs, buckytubes Supramolecular chemistry Materials

6/11/2015Hot Topics and Hypes4 C-H activation Problems: C-H bond is least reactive bond Product is usually more reactive than starting material  further oxidation Product is always better donor than starting material  product inhibition

6/11/2015Hot Topics and Hypes5 C-H activation This will not work:

6/11/2015Hot Topics and Hypes6 C-H activation This does work: B-B bond weak B-H and B-C strong product hardly coordinating

6/11/2015Hot Topics and Hypes7 C-H activation A real example: Electrophilic attack on C-H bond (?)

6/11/2015Hot Topics and Hypes8 CH 4 to CH 3 OH: how does industry do it? "hot pipes"

6/11/2015Hot Topics and Hypes9 CH 4 to CH 3 OH: how does nature do it? (we think) MMO = "methane mono-oxygenase"

6/11/2015Hot Topics and Hypes10 C-H activation C-H activation for CH 4  CH 3 OH via homogeneous catalysis is "useless" selective conversion van non-activated C-H bonds in larger molecules is highly desirable nature does this through "shape selectivity" with e.g. cytochrome P450 zeolites sometimes work quite well

6/11/2015Hot Topics and Hypes11 How can you study C-H activation? "microscopic reversibility" activation of more reactive C-H bonds e.g. aromatic C sp2 -H bonds

6/11/2015Hot Topics and Hypes12 Selective oxidation Epoxidation: does not work for other olefins (allylic C-H bonds are too reactive)

6/11/2015Hot Topics and Hypes13 Selective oxidation Aldehydes / ketones:

6/11/2015Hot Topics and Hypes14 Selective oxidation Desired: Current process: hydroformylation

6/11/2015Hot Topics and Hypes15 Anti-Markovnikov water addition Desired: Current process: via hydroformylation

6/11/2015Hot Topics and Hypes16 Anti-Markovnikov water addition A possible organometallic route:

6/11/2015Hot Topics and Hypes17 (Co)polymerization of functionalized olefins Desired: Problem:

6/11/2015Hot Topics and Hypes18 (Co)polymerisation of functionalized olefins Possible solutions: Late transition metal complexes b.v. Ni/Pd Brookhart Protection of functional group Functionalization after polymerization

6/11/2015Hot Topics and Hypes19 Chiral conversions Noyori / Knowles / Sharpless Precise tuning needed for every new reaction combinatorial catalysis? Few general principles Many "standard" chiral ligands

6/11/2015Hot Topics and Hypes20 Chiral conversions