…Cont'd Classification of OMC: η1 (monohapto) form as a σ ligand &

…Cont’d Classification of OMC
3. Metal allyl
The allyl ligand is often referred to as an “actor” ligand rather than a “spectator”
ligand. It binds to metals in two ways.
 η1 (monohapto) form as a σ ligand &
 η3 (trihapto) form as a σ + π ligand ----a 3-carbon delocalized
allylic system
The π-allyl complex is believed to be formed via the σ-bonded allyl derivatives of the
metal.
M
The σ-cpd is transformed to the π-cpd (η3-allyl complex) by thermal or photochemical
energy. Such a complex is called a fluxional complex; it isomerizes with a little energy.
Eg. η5-(Cyclopentadienyl)-molybdenium tricarbonyl reacts with allyl chloride to form first

the σ-cpd which on warming isomerizes to the π-complex.
CO CH2
CO CO CO
CO CO
Mo CH
+ Mo CH2 CH CH2
CH2
Heat
Cl
CO
CO CO
σ-cpd, yellow oil
Mo
CH
π-cpd, yellow solid

H 2C
(i). In its monohapto (η1) form, it behaves as an anionic 1e−donor type of a
ligand analogous to that of a methyl moiety while
(ii) in a trihapto (η3) form, it acts as an anionic 3e−donor type of a ligand.
Synthesis of the metal allyl complexes
The metal allyl complexes are synthesized by the following methods.
i.From an alkene complex.
ii. By a nucleophilic attack of an allyl compound.

iii. By an electrophilic attack of an allyl compound.
iv. Some allyl complexes are obtained by protonation of. a diene complex.
Eg. From butadiene complexes

Reactions of metal allyl complexes
The reactivities of the metal allyl complexes toward various species are illustrated below.
i.Reaction with nucleophiles
ii. Reaction with electrophiles

iii. Insertion reaction
iv. Reductive elimination

4. Diene complexes
The bonding in a M-butadiane complex may be understood by considering the
two extreme situations.
M M
M The bonding interaction b/n the
The metal & the olefin are metal & the olefin is delocalized
The metal is bonded to the involved in σ,σ,π interaction
two π orbitals π interaction
1,3−Butadiene is a 4e−donor ligand that binds to a metal in a cisoid conformation.
 The Dewar−Chatt model, when applied to 1,3−butadiene, predicts that the ligand
may bind to metal either as a L2 (π2) donor type or as an LX2 (σ2π) donor type.
The L2 binding of 1,3−butadiene is rare, e.g. as in (butadiene)Fe(CO)3, while
the LX2 type binding is more common
An implication of the LX2 type binding is in the observed shortening of the
C2−C3 (1.40 Å) distance alongside the lengthening of the C1−C2 (1.46 Å) &
C3−C4 (1.46 Å) distances.
Fig. Metal−diene interaction in cisoid binding

When butadiene is complexed with a TM, the binding occurs through a combination
of forward & backward donation
Bonding b/n a M & butadiene

π
σ π
σ
M
MOs of
butadiene
2π-bonding & 2π*-antibonding orbitals
The antibonding orbital ψ3 receives e-- density by back donation from the
metal
The central C-C bond is shortened.
Eg. In Butadienetricarbonyl Iron
1.45Ao 1.4
A 5
o
Fe
OC CO
CO
The central C-C bond is (1.45Ao ) is shortened from 1.48Ao in free butadiene.
Though cisoid binding is often observed in metal butadiene complexes, a few
instances of transoid binding is seen in trinuclear, e.g. as in Os3(CO)10(C4H6), &
in mononuclear complexes e.g. as in Cp2Zr(C4H6) .
Fig. Metal−diene interaction in transoid binding.

Metal cyclobutadiene complexes
Cyclobutadiene is an interesting ligand b/c of the fact that its neutral form, being
anti−aromatic (4π−electrons), is unstable as a free molecule, but its
dianionic form is stable because of being aromatic (6π−electrons).
Consequently, the cyclobutadiene ligand is stabilized by significant metal to ligand
π−back donation to the vacant ligand orbitals.
A synthetic route to metal cyclobutadiene complex is shown below.
MO of Cyclobutadiene complex ?
Metal carbonyl compounds
Requirements
 Metal should be in low ox.state 0,1 or 2

i.e., e- rich
 Ligand should – π-acceptor

i.e., e- - donor or acceptor through empty p,π* or d-orbital
CO is a π-acid ligand.

What are π-acid ligands?
Ligands with a pair of electrons available for donation to the metal
centre & vacant orbital p, π*, or d available for accepting electron
density from the metal.
PPh3 , where Ph= C6H5 is also such a ligand
The carbonyl ligand is a π-acid in the Lewis sense, where it receives electrons
from the metal ion, & it is a π–acid because this involves π-bonding.
The π-bonding involves overlap of the π* orbitals of the CO with d orbitals from
the t2g set of the metal, & so is dπ-pπ bonding.
The structures involved in the π-acid nature of CO are:
What stabilizes CO complexes? It is M→C π–bonding.
The lower the formal charge on the metal ion, the more willing it is to donate
electrons to the π–orbitals of the CO. Thus, metal ions with higher formal
charges, e.g. Fe(II) form CO complexes with much greater difficulty than do zero-
valent metal ions such as Cr(O) & Ni(O), or negatively charged metal ions such
as
V(-I).
The π–overlap is pictured as involving d-orbitals of the metal & the π*–
orbitals of the CO:
2p
Bonding
Sequence of bonding
1st A pair of e- is donated from the π-acid to the metal centre.
Then, the excess e- density around the metal centre is donated back
to the empty orbitals on the ligand.
 CO donates 2e-s to the system from the σnb orbitals on C.
The HOMO & LUMO of CO
M-CO’s are important for their rich properties & applications in many industrial
processes that include :
 catalysis,
 medical diagnostics &
 molecular sensors
Mond process,1890
Ni(CO)4 → Ni0 + 4CO
Mononuclear
 Metal carbonyls
polynuclear
END OF SESSION 4

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…Cont’d Classification of OMC

Eg. η5-(Cyclopentadienyl)-molybdenium tricarbonyl reacts with allyl chloride to form first

π-cpd, yellow solid

ii. By a nucleophilic attack of an allyl compound.

Eg. From butadiene complexes

ii. Reaction with electrophiles

iv. Reductive elimination

1,3−Butadiene is a 4e−donor ligand that binds to a metal in a cisoid conformation.

the LX2 type binding is more common

C3−C4 (1.46 Å) distances.

Fig. Metal−diene interaction in cisoid binding

Bonding b/n a M & butadiene

in mononuclear complexes e.g. as in Cp2Zr(C4H6) .

Fig. Metal−diene interaction in transoid binding.

 Metal should be in low ox.state 0,1 or 2

 Ligand should – π-acceptor

CO is a π-acid ligand.

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