Organometallic Reaction Summary
Reaction
Type
Basic
Reaction
Format
Requirements Key Features
Metal
Center:
Before →
After
MLₙ →
MLₙ ₋₁L'
Metal/Species
Before and
After
Ligand
Substitution
MLₙ + L' →
MLₙ ₋₁L' + L
Coordination
site or ligand
lability
Oxidative
Addition
MLₙ + X–Y
→ MLₙ XY
(oxidation
state ↑)
Low-valent,
electron-rich
metal center
Reductive
Elimination
MLₙ XY →
MLₙ + X–Y
(oxidation
state ↓)
Ligands X and
Y must be cis
and adjacent
σ-Bond
Metathesis
M–R + H–R'
→ M–R' +
H–R
d⁰ or f-block
metals; X–H
bond present
Alkyl
Migration
M–R + L=Z
→ M–(Z–R)
Alkyl and
unsaturated
ligand must
be cis
Dissociative
or associative;
maintains
oxidation
state
Increases
oxidation
state and
coordination
number
Decreases
oxidation
state; forms
new covalent
bond
Concerted 4center
transition
state; no
oxidation
change
Migratory
insertion;
forms new C–
C or C–Z bond
MLₙ →
MLₙ XY
(oxidation
↑)
MLₙ (lowvalent) →
MLₙ XY (highvalent)
MLₙ XY →
MLₙ
(oxidation
↓)
MLₙ XY (highvalent) →
MLₙ (lowvalent) + X–Y
No change
in metal
oxidation
M–R + H–R' →
M–R' + H–R
(metal
unchanged)
MLₙ →
MLₙ (with
new R–Z)
M–R + L=Z →
M–(Z–R)
(insertion
product, no
oxidation
change)
M–H + alkene
→ M–CH₂–
CHR (hydride
shift, metal
unchanged)
M–alkyl (with
β-H) → M–H +
alkene (metal
unchanged)
M–CH₂R →
M=CHR + H⁻
(metal center
forms metalcarbene)
Hydride
Migration
M–H + C=C
→ M–CH₂–
CHR
Metal–
hydride + πbonded
alkene
Hydride adds
MLₙ →
to alkene;
MLₙ H–C–C
initiates
hydrogenation
β-Hydrogen
Elimination
M–CH₂–CH₃
→ M–H +
CH₂=CH₂
α-Hydrogen
Abstraction
M–CH₂R →
M=CHR +
H–
β-H present
on
coordinated
alkyl
α-H present
and suitable
electronic
conditions
Common
termination
step; forms
alkene
Forms metalcarbene; often
needs base or
abstraction
agent
ML–CH₂CH₃
→ ML–H
ML–CH₂R →
ML=CHR
MLₙ →
MLₙ ₋₁L'
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