Organometallic Chemistry Reactions and Catalysis

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Organometallic Chemistry an overview of structures and reactions

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Presentation transcript:

Organometallic Chemistry Reactions and Catalysis Chapter 14 Organometallic Chemistry Reactions and Catalysis

Types of Reactions Ligand loss or gain Ligand modification Dissociation/Substitution Oxidative addition Reductive elimination Nucleophilic displacement Ligand modification Insertion Carbonyl insertion (methyl migration) Hydride elimination Abstraction

Types of Reactions: Dissociation, Addition and Substitution

Aside: olefin = alkene metathesis = exchange of bonds 2005 Nobel Prize

Dissociation of Phosphine Ligands: Steric Effects

Dissociation of Phosphine Ligands: Steric vs. Electronic Effects

Types of Reactions: Oxidative Addition/Reductive Elimination

Oxidative Addition Coordination #’s and Oxidation States?

Special Case: Cyclometallation (orthometallation)

Reductive Elimination: Key usefulness– forms a new bond H-H, C-H, C-X (X = halide, amide, alkoxide, othes) Rates depend on electronic and steric effects. Electronic effects: more weakly bonded ligands are eliminated faster.

Steric Effects: Rate of reductive elimination as a function of other ligand’s “bite angle”

Pd-catalyzed Cross-Coupling reactions: 2010 Nobel Prize Overall Organic Reaction?

Pd-catalyzed Cross-coupling reactions Step 1? Step 2? Step 3: transmetallation substitution adding –R or –Ar to the Pd(II) center Step 4? Step 5?

Pd-catalyzed Cross-coupling reactions

Pd-catalyzed Cross-coupling reactions

Current Research Area: Pincer Ligands

Ligand Modification Reactions: Insertion Reactions Examples:

Ligand Modification Reactions: Carbonyl Insertion Possible Mechanisms: Propose mechanisms and examine experimental results.

Possible Mechanisms:

Possible Mechanisms:

Possible Mechanisms:

Experimental Evidence:

Which mechanism is best supported? Analyze Mechanism 1. Is this a plausible mechanism? Compare Mechanisms 2 and 3. Which is better supported by the evidence.

1. Analyze Mechanism 1. Is this a plausible mechanism?

2. Compare Mechanisms 2 and 3: Use reverse reaction results

2. Compare Mechanisms 2 and 3: Use reverse reaction results

1,2-olefin Insertion Reactions

Hydride Elimination (-elimination) What is the reverse reaction?

Catalysis: Deuteration

Catalysis: Hydroformylation

Catalysis: Hydroformylation

Turnover Frequency http://pubs.acs.org/doi/pdf/10.1021/om100552h Turnover Number: http://pubs.acs.org/doi/abs/10.1021/om060605p