Chapter 14 Organometallic Chemistry Reactions and Catalysis Types

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Chapter 14 Organometallic Chemistry Reactions and Catalysis

Chapter 14 Organometallic Chemistry Reactions and Catalysis

Types of Reactions • Ligand loss or gain • Dissociation/Substitution • Oxidative addition •

Types of Reactions • Ligand loss or gain • 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

Types of Reactions: Dissociation, Addition and Substitution

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

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

Dissociation of Phosphine Ligands: Steric Effects

Dissociation of Phosphine Ligands: Steric Effects

Dissociation of Phosphine Ligands: Steric vs. Electronic Effects

Dissociation of Phosphine Ligands: Steric vs. Electronic Effects

Types of Reactions: Oxidative Addition/Reductive Elimination

Types of Reactions: Oxidative Addition/Reductive Elimination

Oxidative Addition Coordination #’s and Oxidation States?

Oxidative Addition Coordination #’s and Oxidation States?

Special Case: Cyclometallation (orthometallation)

Special Case: Cyclometallation (orthometallation)

Reductive Elimination: Key usefulness– forms a new bond H-H, C-X (X = halide, amide,

Reductive Elimination: Key usefulness– forms a new bond H-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”

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: 2010 Nobel Prize Overall Organic Reaction?

Pd-catalyzed Cross-coupling reactions Step 1? Step 2? Step 3: transmetallation substitution adding –R or

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

Pd-catalyzed Cross-coupling reactions

Pd-catalyzed Cross-coupling reactions

Current Research Area: Pincer Ligands

Current Research Area: Pincer Ligands

Ligand Modification Reactions: Insertion Reactions Examples:

Ligand Modification Reactions: Insertion Reactions Examples:

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

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

Possible Mechanisms:

Possible Mechanisms:

Possible Mechanisms:

Possible Mechanisms:

Possible Mechanisms:

Possible Mechanisms:

Experimental Evidence:

Experimental Evidence:

Which mechanism is best supported? 1. Analyze Mechanism 1. Is this a plausible mechanism?

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

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

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

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

1, 2 -olefin Insertion Reactions

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

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

Catalysis: Deuteration

Catalysis: Deuteration

Catalysis: Hydroformylation

Catalysis: Hydroformylation

Catalysis: Hydroformylation

Catalysis: Hydroformylation

Turnover Frequency http: //pubs. acs. org/doi/pdf/10. 1021/om 100552 h Turnover Number: http: //pubs. acs.

Turnover Frequency http: //pubs. acs. org/doi/pdf/10. 1021/om 100552 h Turnover Number: http: //pubs. acs. org/doi/abs/10. 1021/om 060605 p

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