TYPES OF REACTIONS

Oxidative addition
• In oxidative addition, a metal complex with vacant coordination sites and
a relatively low oxidation state is oxidized by the insertion of the metal
into a covalent bond (X － Y)
• Both the formal oxidation state of the metal and the electron count of the
complex increase by two
• Oxidative additions can occur with the insertion of a metal into many
different covalent bonds, they are most commonly seen with H － H and
Csp3 － halogen bonds
 Reductive elimination
• A reductive elimination involves the elimination or expulsion of a molecule
from a transition metal complex
• In the process of this elimination, the metal center is reduced by two
electrons
• The groups being eliminated must be in a mutually cis orientation
• A series of reactions involving an oxidative addition, a rearrangement and
then a reductive elimination form the basis for a variety of industrially
important catalytic cycles
 Transmetalation
• Transmetalation is a general chemical reaction type describing the
exchange of ligands between two metal centers
• The metal centers need not be the same
• The ligands R and R' can be organic or inorganic

• Transmetalation is important in the synthesis of various organometallic

compounds. This reaction type also appears frequently in the catalytic cycle
of various metal catalyzed organic reactions.
 Carbometalation
• Carbometalation is an reaction involving the nucleophilic addition to
alkenes and alkynes of a diverse range of organometallic reagents such as
organolithium compounds, organocopper compounds and Grignard
reagents according to the following general alkyne scheme:
 Migratory insertion
• A migratory insertion reaction is when a cisoidal anionic and neutral ligand
on a metal complex couple together to generate a new coordinated
anionic ligand
• This new anionic ligand is composed of the original neutral and anionic
ligands now bonded to one another
• No change in formal oxidation state (exception: alkylidenes), alkynes,
carbenes
• The two groups that react must be cisoidal to one another
• A vacant coordination site is generated by the migratory insertion
• Migratory insertions are favored on more electron-deficient metal centers
 Alkene Migratory Insertions
• Alkene and hydride/alkyl migratory insertion is the basis for almost all
transition metal-based polymerization catalysts

• A polymerization is just many, many migratory insertions of an alkene and

alkyl (the growing polymer chain) interspaced with alkene ligand addition
reactions
• An alkene and a hydride usually react via a migration of the hydride to the
coordinated alkene ligand:

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

favorable if there is an empty orbital cis to the alkyl ligand
• Thus, the general importance of having a trapping ligand to coordinate to
the empty orbital generated from the migratory insertion
 β-Hydride elimination
• Elimination reactions are just the reverse of migratory
insertion reactions
• β -Hydride elimination is a reaction in which an alkyl
group bonded to a metal centre is converted into the
corresponding metal-bonded hydride and an alkene
• No change in formal oxidation state (exception: alkylidenes)
• A vacant orbital is cisoidal to the group to do an elimination reaction on.
Alternatively, a cisoidal labile ligand that can easily dissociate to open up an
empty orbital.

Avoiding β-hydride elimination:

i. to employ an alkyl ligand that lacks a β-hydrogen (methyl or neopentyl)
ii. It is also inhibited when the reaction would produce a strained alkene
iii. The beta position may be blocked by non-hydrogen atoms
iv. If the metal center does not have empty coordination sites, for
example, by the complex already having 18 electron configuration, β-
hydride elimination is not possible as well
 α-Hydride Elimination
• A less common reaction with metal alkyls is the α-hydride elimination, where
a hydrogen atom on the α-carbon is added to the metal to generate a
M=CR2 (carbene or alkylidene) group and a hydride:

• It is important to have an empty orbital cis to the α-hydrogen in order to have

the αhydride elimination occur
 Reaction Mechanisms - Ligand Substitutions
• A substitution reaction is one in which an existing ligand on a metal center is
replaced by another ligand
• Exactly how this occurs depends on the electron count of the metal complex,
the existing ligands on the metal, and their steric and electronic properties

• The mechanism of this substitution will almost always depend on whether the
parent MLn complex is coordinatively saturated or not
• Substitutions reactions occur by a combination of ligand addition and ligand
dissociation reactions
• Saturated Complex: Dissociative Pathway
• Unsaturated Complex: Associative Pathway (usually)
Dissociative pathway (sometimes)
• Most of the substitutions involve 2e- pathways.
• Odd e- or radical pathways are known, but less common
 Ligand Addition (association)

• This is when an incoming ligand coordinates to a metal center that has

one or more empty orbitals available

• This Rh(+1) complex is d8 and only 14e-

• Adding a ligand takes one to the more stable 16e- square-planar complex
 Ligand Dissociation
• This is when a ligand coordinated to a metal dissociates (falls off)
• The probability of a specific ligand dissociating depends on how strongly
or weakly it is coordinated to the metal center and steric effects
• A ligand substitution can occur either by an associative or dissociative
route
• The exact mechanism depends in large part on the electron-count of the
metal complex undergoing the ligand substitution
• The simplest case is when one is dealing with an 18e- metal complex
• In this case one almost always has a dissociative substitution
• In a dissociative substitution, one of the existing ligands on the metal
center has to fall off (ligand dissociation), this opens up a free coordination
site (16e-, if one started from an 18e- complex) to which the new ligand can
coordinate
• 18e- complexes almost always do ligand substitutions through initial ligand
dissociation
• Dissociative substitution can also occur in 16e- (or in very unusual cases,
lower electron count systems) complexes
• These cases either involve sterically bulky ligands that block the open
coordination site, or third row square planar d8 complex like Pt(+2) where
there are strong electronic factors that limit the coordination of an additional
ligand to the empty axial site
 Steric Factors
• Bulky (large) ligands occupy more space around a metal center and can
block incoming ligands trying to access vacant coordination sites on a
metal
• Due to steric hindrance, however, they are also more often to dissociate to
relieve the steric strain
• Consider, for example, the following equilibrium:

Note that there is virtually no Ni(PPh3)4 in solution. There is too much

steric hindrance with the bulky PPh3 ligands.
 Solvent Effects
• Consider the following dissociative substitution reaction

• The 14e- three coordinate intermediate is actually almost immediately

coordinated by a solvent molecule to produce the solvated 16e- complex
• The solvent is usually weakly coordinated and readily dissociates to
constantly produce the 14e- reactive intermediate
• The coordinating ability of the solvent, therefore, can often affect reactions
• The presence of lone pairs and electron-rich donor atoms on the solvent
usually makes it a better ligand
• The polarity of the solvent can also have a definite impact on a reaction
• Polar solvents are usually quite good for reactions, that involving charged
species
• A non-polar hydrocarbon solvent (like toluene, for example) would probably
inhibit the chloride dissociation mechanism
• Instead, the dissociation of the neutral, less polar phosphine ligand would
probably be favored
• Note that one often avoids oxygen containing solvents due to the reactivity
of early transition metals towards them
• Water is rarely used in organometallic chemistry since many of the
reactive metal-alkyl complexes are basic enough and will readily react with
water
• Non-coordinating solvents are a misnomer since anything can coordinate
to a metal center that is unsaturated and electron-deficient
• Saturated hydrocarbons like hexane are classic “noncoordinating”
solvents
• Arene solvents can coordinate via their π-systems, but usually not too
strongly
• A common less coordinating, but polar solvent, is CH2Cl2, which is one of
the less reactive chlorocarbon solvents
• Chlorobenzene is another relatively non-reactive, but somewhat polar
solvent
 Trans Effect
• The trans effect concerns the electronic effect of one ligand on another ligand
when they are trans to one another
• The classical trans effect involves two σ-donating ligands trans to one
another
• The stronger σ-donor ligand preferentially weakens the bond of the weaker σ-
donor ligand trans to it, making it easier to dissociate and do a ligand
substitution reaction
 π-Acceptor Trans Effects
• The bonding of a π-backbonding ligand to a metal with two or more d
electrons is weakened when there is a trans π-backbonding ligand
• The competition of both π-backbonding ligands for the same d orbital
electrons reduces the amount of π-backbonding that can occur and,
therefore, weakens the M-CO bond strength

• Conversely, a π-backbonding ligand bonding to a metal is strengthened by

being trans to a good σ-donating ligand that can’t π-backbond
• Compare the CO infrared stretching frequencies for the following two
complexes:

• The P(OMe)3 ligand has about the same σ-donor ability as pyridine, but
is a considerably better π-acceptor ligand, thus competing with the trans
CO ligands more than the pyridine ligands
• There is a further strengthening of M-CO π-backbonding when the trans
ligand has π-donation properties that can push up the energy of the filled
d orbitals and, in turn, make them better π-donors to the CO
• This can occur even when the ligand is not an especially strong donor
 An example of this can be seen in the following three complexes and
their “anomalous” νCO stretching frequencies:

Even though the trans PPh2 is a better σ-donor than the P=S, or certainly the
P=O ligand, the “π-pushing” effect mentioned above enhances the trans CO π-
backbonding for the P=S and P=O ligands.
 Associative Substitutions
• These occur first by a ligand addition to the metal complex followed by the
dissociation of one of the original ligands
• need to have an unsaturated (17e- or lower) complex in order to propose an
associative substitution mechanism

• The filled axial Pt dz2 orbital partially blocks coordination of ligands via the
empty axial pz orbital.
• This limits, but does not stop ligand association, which is quite common for
Rh(I) and Pd(II)
• Although one could theoretically have a ligand addition to an 18e- complex
to form a 20e- transition state (or intermediate) that would then dissociate a
ligand to reform an 18e- system, there are very few verified examples of this
in the literature

• So associative substitutions are generally limited to 17e- and lower electron-

count systems where the incoming ligand is not sterically or electronically
blocked from bonding (coordinating) to the metal center
 “AC/DC” Ligands
• Multidentate ligands (those donate more than 2e- and occupy more than
one coordination site on a metal) can often change their coordination
number to donate fewer electrons, thus opening up a coordination site that
can allow an associative substitution (or just ligand addition)
• The Cp ligand can do this by shifting from an η5 to η3 (or even η1)
coordination mode as shown in the example below:

But shifting the η5-Cp to the η3-Cp coordination mode incurs a moderately high
energy cost due to the loss of aromaticity in the Cp ring. So this is not that
common
 Reference work
• Indenyl Effect
• Pentadienyl
• Allyl
• Nitrosyl
• Radical Odd Electron Systems
• Electron Transfer Catalysis (ETC)
 Electron Transfer Catalysis (ETC)
• One can “force” a stable, kinetically inert 18e- complex into a considerably
more reactive state by oxidizing it to a 17e- configuration, thus opening up
half a free orbital to which a ligand can bind initiating a ligand substitution
reaction. The metal can then be reduced back to the 18e- state
• Or one could reduce the metal to an unstable 19e- state, which would
labilize off the weakest coordinated ligand taking the metal complex down
to a more reasonable 17e- count. The metal center can then be oxidized
back to a 16e- state, giving an open orbital for a new ligand to coordinate
• This is usually done electrochemically and since there is no net change in
the number of electrons on the metal (oxidation is followed by reduction), it
is considered a catalytic substitution reaction