8/4/2022

Types of Reactions

• Ligand loss or gain

• Ligand Substitution Reactions
• Oxidative addition
Organometallic • Reductive elimination
• Ligand modification
Reactions • Carbonyl insertion (methyl migration)
• β-Hydride elimination

Ligand Substitution Rxns Ligand Substitution Reaction

MLn + xP MLn-xPx + xL

• Mechanism depends on MLn complex is

coordinatively saturated or not!

• Saturated Complex: Dissociative Pathway (D)

• Unsaturated Complex: Associative Pathway (A) (usually)
Dissociative pathway (sometimes)
• Most of the substitutions involve 2e- pathways.
• Odd e- or radical pathways are known.

1
 8/4/2022

Associative Substitutions
• a ligand addition to the metal complex followed by the Dissociative substitution
dissociation of one of the original ligands.
• Need to have an unsaturated (17e- or lower) complex for • stable ligands (CO, olefins, Cl-) dissociate easily
associative substitution mechanism. (as opposed to e.g. CH3, Cp).

O O O
C C C
-CO +PMe3
OC CO OC CO OC CO
Mo Mo Mo
OC CO OC CO OC CO
C PMe3
O
18e- saturated 16e- unsaturated 18e- saturated
complex complex complex

Oxidative Addition/Reductive Elimination

 OA -a neutral ligand adds to a metal center
 oxidizes the metal by 2e-.
 The transferring of the 2e- from the M to the incoming L breaks
a bond in that ligand forming two new anionic ligands.
 At least one of these new anionic ligands ends up bonded to the
metal center. two new anionic
hydride ligands

H H H
OC PPh3 +H2 OC PPh3 OC PPh3
Ir Ir Ir
Ph3P Cl Ph3P Cl Ph3P H
Cl
Ir(+1) Ir(+1) Ir(+3)
16e- 18e- 18e-

2
 8/4/2022

Oxidative Addition C-H activation

Reductive Elimination, RE RE
 A RE is the reverse of OA.
 two cisoidal anionic ligands on a metal center couple together.
 Each anionic ligand pushes one electron back onto the metal center to H-H, C-H, C-X (X = halide, amide, alkoxide, othes)
reduce it by 2e-.
 The coupled anionic ligands fall off the metal center as a neutral Rates depend on electronic and steric effects.
molecule.

Electronic effects:
more weakly bonded ligands are eliminated faster.
Steric Effects: Rate of reductive elimination as a
function of other ligand’s Steric factor

3
 8/4/2022

Pd-catalyzed Cross-Coupling reactions: 2010 Nobel Prize Pd-catalyzed Cross-coupling reactions: 2010 Nobel Prize
Step 1: OA

Step 2: cis-trans isomerization

Step 3: transmetallation
substitution adding –R or –Ar
to the Pd(II) center

Step 4: cis-trans isomerization

Step 5: RE

Overall Organic Reaction?

Hydride Elimination (-elimination)

Migratory Insertion

What is the reverse reaction?

4
 8/4/2022

 A migratory insertion reaction - a cisoidal anionic and

neutral ligand on a metal complex couple together to
generate a new coordinated anionic ligand.  Common anionic and neutral ligands undergo
migratory insertion :
migratory insertion ligand addition
acyl
 Anionic: H-, R- (alkyl), Ar- (aryl), acyl-, O2- (oxo)
O O CH3 O CH3
C  Neutral: CO, alkenes, alkynes, carbenes
OC CO OC CO +L OC CO
Mn Mn Mn
OC CH3 OC OC L
C C C  CO and alkyl migratory insertions referred to as
O O O carbonylation reactions.
Mn(+1) Mn(+1) Mn(+1)
18e- 16e- 18e-
elimination

Migration

O O CH3
C a MIGRATION rxn involves the
OC CO OC CO anionic ligand doing a
Mn Mn nucleophillic-like attack on the
OC CH3 OC neutral ligand. This involves the
 General Features of Migratory Insertions: C
O
C
O
anionic ligand moving to the site
where the neutral ligand is
coordinated. An empty
1. No change in formal oxidation state Mn(+1) Mn(+1) coordination site is left behind.
18e- 16e-
2. The two groups that react must be cisoidal to one
Insertion
another O
C an INSERTION rxn involves the
3. A vacant coordination site is generated by the migratory OC CO OC CO neutral ligand moving over to
Mn Mn where the anionic ligand is
O
insertion OC CH3 OC coordinated and "inserting" into
C C the anionic ligand-metal bond to
CH3 generate the new anionic
4. Migratory insertions are usually favored on electron- O O
ligand. An empty coordination
deficient metals. Mn(+1)
18e-
Mn(+1)
16e-
site is left behind from where
the neutral ligand originally was
located.

5
 8/4/2022

1,2-olefin Insertion Reactions  An alkene and a hydride usually react via a migration of the hydride to
the coordinated alkene ligand:

migratory insertion

H
H H H H ‡ H
H
H H H H H H

M H M H M

-hydride elimination

 The backwards reaction, is a ᵦ-hydride elimination and is usually quite

favorable if there is an empty orbital cis to the alkyl ligand.

 β Hydride elimination (usually by b hydrogens)

Eliminations
 Elimination reactions are just the reverse of migratory insertion reactions. The various common elimination  Many transition metal alkyls are unstable (the reverse of insertion)
reactions are as follows:  the metal carbon bond is weak compared to a metal hydrogen
H
H
H
 Bond Alkyl groups with β hydrogen tend to undergo β elimination
H -hydride elimination
M
M  M -CH2-CH3  M - H + CH2=CH2

H H
H -hydride elimination
M M
R
R

O
R carbonyl elimination
M or decarbonylation
M CO
R

6
 8/4/2022

1. No change in formal oxidation state (exception:

alkylidenes)
2. Must have an empty orbital that is cisoidal to the
group that you are doing an elimination reaction
on. Alternatively, a cisoidal labile ligand that can
easily dissociate to open up an empty orbital.
 One of the hardest elimination reactions is the breaking
of a C-C bond.