Pi Acid Ligands

Definition

The pi acceptor or acid ligands are those which possess vacant

pi orbitals in addition to lone pairs of electrons.
These ligands are those which donate their lone pair of
electrons to the metal to form a normal σ bond with the latter.
In addition to this vacant orbitals accept electrons from the
filled metal orbitals to form a type of pi bond which
suppliments σ bond. These ligands are called as pi acceptor or
acid ligands. Common examples are CO, NO, PR3, CNR etc.
 Carbon Monoxide Complexes

Metal carbonyls are coordination compounds formed between the

electron donor CO groups and the transition metals such as Ni,
Fe and Co.

The first carbonyl formed was Ni (CO)4 by L. Mond in 1889.

Then Fe (CO)5 was reported.

 METAL CARBONYLS

• Compounds having at least one bond between carbon and metal

are known as organometallic compounds.
• Metal carbonyls are the transition metal complexes of carbon
monoxide containing metal-carbon bond.
• Lone pair of electrons are available on both carbon and oxygen
atoms of carbon monoxide ligand. However, as the carbon
atoms donate electrons to the metal, these complexes are named
as carbonyls.
• A variety of such complexes such as mono nuclear, poly nuclear,
homoleptic and mixed ligand are known.
 METAL CARBONYLS

• The carbonyl ligand is a π-acid. This is an acid in the Lewis

sense, where it receives electrons from the metal ion, and 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, and so is dπ-pπ bonding (VBT) or dπ- π* (MOT).
The canonical structures involved in the π-acid nature of CO are:

δ+ δ-

M­C≡O M=C=O
 METAL CARBONYLS

• Carbon monoxide is one of the most important π- acceptor

ligand. Because of its π- acidity, carbon monoxide can
stabilize zero formal oxidation state of metals in carbonyl
complexes.
TYPES OF METAL CARBONYLS
Mononuclear
Binuclear
Polynuclear
 METAL CARBONYLS

Table: Different types of metal carbonyls

Type Examples

Mononuclear carbonyls [Ti(CO)6]-2, [V(CO)6],

[Cr(CO)6], [Fe(CO)5],

[Ni(CO)4]

Binuclear carbonyls [Mn2(CO)10], [Fe2(CO)9],

[Co2(CO)8]

Polynuclear carbonyls [Fe3(CO)12], [Co4(CO)12],

 Mononuclear Metal Carbonyls

• Mononuclear metal carbonyls have all the terminal carbonyl

CO groups. The shapes are those expected from the formula.
E.g. Ni(CO)4 has tetrahedral structure.
• Cr(CO)6 has octahedral structure
• Fe(CO)5 have trigonal bipyramidal shape.
 Binuclear Metal Carbonyls

• Binuclear metal carbonyls show metal- metal bonding and

bridging carbonyl CO groups in their molecules.
•
 Polynuclear metal carbonyls

• Metals such as Fe, Mn, Co, etc. forms a number of

polynuclear metal carbonyls in which the metal ion is either
linked directly through metal-metal bonds as in Mn2(CO)10 or

through bridging carbonyl groups as in Co2(CO)8.

 M4(CO)12
POLYNUCLEAR CARBONYL COMPLEX
 Bonding in linear MCO groups

In order to understand the bonding first review the MOT of CO.

Since the σ3(nb) is the HOMO localised on the carbon atom. It results in
the formation of dative σ-bond:

The overlapping of empty hybrid orbital (a blend of d, s and p orbitals)

on metal atom with the filled hybrid orbital (HOMO) on carbon atom
of carbon monoxide molecule results into the formation

of a M←CO σ-bond.
LUMO is π* antibonding molecular orbital of CO.
d π- π* overlap is there.
In addition to formation of additional pi bond between M-CO,

d π- π* bond also

i) Stabilises or strengthen the M-C bond (By removing excessive negative charge on
metal ion)

ii) Shows synergistic effect. (metal and ligand comes closer. One bond makes other
stronger)

iii) Reduces the bond order of CO- one way increases M-C bond but other way
weakens the CO bond.

iv) M-C bond order increases in the order in the case of iso-electronic and iso-
structural species such as

[Ni(CO)4], [Co(CO)4]- and [Fe(CO)4)]2-

Ni-C ˂ Co-C ˂ Fe-C

Simultaneously C-O decreases in the order [Ni(CO)4]˃ [Co(CO) 4]- ˃ [Fe(CO)4)]2-

Symmterically bridged, asymmetrically bridged and tribridged
What stabilizes CO complexes 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

For example Cr(0) and Ni(0), or negatively charged metal

ions such as V(-1)

In general to get a feeling for stability examine the charges

on the metals
Gives valuable support for bonding in metal carbonyls. These studies provide
information about bond orders of M---C and CO bonds.
 IR spectra and metal-carbon bonds
The υCO stretching frequency of the coordinated CO is very
informative
Recall that the stronger a bond gets, the higher its stretching
frequency
M=C=O (C=O is a double bond) canonical structure
Lower the υCO stretching frequency as compared to the M-C≡O
structure (triple bond)
Note: υCO for free CO is 2041 cm-1)

[Ti(CO)6]2- [V(CO)6]- [Cr(CO)6] [Mn(CO)6]+ [Fe(CO)6]2+

υCO 1748 1858 1984 2094 2204 cm-1

increasing M=C double decreasing M=C double

bonding bonding
 Bridging versus terminal carbonyls

Bridging CO groups can be regarded as having a double bond

C=O group, as compared to a terminal C≡O, which is more like a
triple bond:
~ double bond the C=O group
~ triple bond in a bridging
carbonyl is more
M like the C=O in
a ketone, which
M-C≡O C=O typically has
M υC=O = 1750 cm-1

terminal carbonyl bridging carbonyl

(~ 1850-2125 cm-1) (~1700-1860 cm-1)
Bridging versus terminal carbonyls in [Fe2(CO)9]
O
CO
OC
C
CO
Fe
OC Fe
C
C O
OC CO

terminal bridging
carbonyls carbonyls
Summary

1. As the CO bridges more metal centers its stretching

frequency drops – same for all p ligands
– More back donation
2. As the metal center becomes increasingly electron rich the stretching frequency
drops
 IR spectroscopy

• Determination of geometry of mononuclear metal

carbonyls
• Determination of bond order of CO bond
• Any factor which increases the electron density on the pi
antibonding orbital of the ligated CO would decrease the bond
order of CO and hence vibrational frequency of CO bond while the
one which decreases the electron density would do the reverse.
• Differentiating between Terminal and Bridging carbonyl
– 2050-1900 cm-1 for terminal and 1900- 1800 cm-1 for bridging

– Study of reaction rates

– By measuring the rates of decrease of intensity of CO absorption bands
in IR spectra of carbonyls
 INERT GAS RULE/ 18-ELECTRON RULE

• A complex in which the central metal atom appears to have

acquired configuration of an inert gas by transference or
sharing of electrons tends to be more stable.
• Acc. To EAN rule, the effective no. of electrons in the n-1 d.
ns and np orbitals of a transition metal in its complex should
be equal to 10+2+6 =18. this means the total no. of electrons
acquired by the metal through the covalent or coordinate
bonding with the ligands plus the no. of original electrons in
the valence shells of metal prior to its complexation should be
equal to 18. this is known as 18 electron rule.
 Counting the effective number of electron

1. Count the number of electrons in the valency shell of the free

metal atom. Add or subtract the electrons as per the charge on
the metal atom in the complex.
2. Check the no. of electrons which the ligands contributes to the
metal atom.
3. Check the number of electrons formally contributed to the
valency shell of the metal by the metal metal bonds. Each M-
M bond contributes one electron to the valency shell of the
metal in the complex.
Add 1, 2,3 = effective no. of electrons in the valence shell of the
metal in the complex.
 INERT GAS RULE/ 18-ELECTRON RULE

• Fe(CO)5

• Mn2(CO)10
• Fe2(CO)9(contains 3 CO bridges)

• [Mn(CO)5C2H4]+ (Olefines act as 2 electron donor)

• Mo(CO)6 (Z=42)
• V(CO)6
Metal carbonyl hydrides and halides
 CHEMICAL PROPERTIES

The metal carbonyls give a variety of chemical reactions.

Ligand substitution reactions:
Substitution of carbon monoxide ligand by various mono dentate and
bidentate ligands can be carried out using thermal (upto 200ºC) and
photochemical reactions. Monodentate ligands like isocyanides
(CNR), cyanide (CN-), phosphine (PR3) can partially or completely
replace the carbonyl group.

Fe (CO)5 + PPh3 → PPh3Fe(CO)4 and (Ph3P)2 Fe(CO)3

Ni (CO)4 + 2PPh3 → Ni(CO)2 (Ph3P)2 + 2CO

Fe (CO)5 +2CNR→ Fe (CO)3 (CNR)2 +2CO

Manganese carbonyl is usually resistant to substitution reaction
but under irradiation gives

Mn2 (CO)10 + 2PR3 → [Mn(CO)4 PR3]2+2CO

In the presence of pyridine, heat and UV radiation

Mo(CO)6+ py → Mo(CO)5py + py →Mo(CO)4py2 +py

→Mo(CO)3py3

2Fe(CO)12+3py → Fe3(CO)9(py)3+3Fe(CO)5

Fe(CO)5 +2C5H5 → [(η5C5H5)Fe(CO)2]

 Formation of Carbonylate ions

It can be obtained by number of ways:

– By treating the carbonyls with alc. or aqueous alkali
hydroxides or amines, sulfoxides or with other lewis bases,
by cleaving M-M bonds with Na or in special cases by
refluxing carbonyls with salts in an ether medium.
 CHEMICAL PROPERTIES

Reaction with metallic sodium:

Metallic sodium and its amalgam in liq. NH3 can be used to reduce the
metal carbonyls to carbonylate anion

Co2(CO)8 +2Na/Hg THF→ 2Na[Co(CO)4]

Cr(CO)6 +2Na → Na2 [Cr(CO)5 ]+ CO

Mn2 (CO)10 +2Na → 2Na[Mn(CO)5 ]

In the above two reactions, the Cr and Mn atoms in their zero oxidation
states are reduced to -2 and -1 oxidation states respectively.
 Carbonyl hydrides
Reaction with sodium hydroxide:
The reaction of sodium hydroxide with metal carbonyls results in
nucleophilic attack by hydroxide ion on the carbonyl group to give
a metal carboxylic acid complex. Upon further action with sodium
hydroxide, the carboxylic acid gives up carbon dioxide to form a
hydrido anion. The protonation of this anion results in the formation
of iron tetracarbonyl hydride as shown below:

Fe(CO)5 + NaOH → Na[Fe(CO)4COOH]

Na[Fe(CO)4 COOH]+ NaOH → Na[HFe(CO)4] + NaHCO3

Na[HFe(CO)4]+ H+ → (H)2 Fe(CO)4 + Na+

The above reaction is known as Heiber base reaction.

 Carbonyl hydrides
Reaction with hydrogen:
Some of the carbonyls can be reduced by hydrogen to give carbonyl
hydrides

Co2(CO)8 +H2 at165oC, 200 atm → 2[Co(CO)4H]

Mn2(CO)10+H 2 at 200 atm→ 2[Mn(CO)5H]

Even though, these compounds are named as hydrides, they are known
to behave as proton donors. The neutral hydrides like [Co(CO) 4H]

and [Mn(CO)5H] behave as conjugate acids of carbonylate ions as

shown below:

[Co(CO)4H] → [Co(CO)4]- + H +

[Mn(CO)5H] → [Mn(CO)5]- + H+
Methods of preparing selected hydrido complexes
Metal hydride play an important role in
organometallic chemistry and scheme
given illustrate some ligand
transformation involving M-H bonds.
H[Co(CO)4] is a industrial catalyst and
mononuclear hydrido carbonyl anions
include [HFe(CO)4]- and [HCr(CO)5]-
both of which can be made by the diazomethane
action of hydroxide on the parent metal naphthalene
carbonyl
• The reaction of hydrogen gas with a complex Ir(CO)L2Cl (L=
PPh3) leads to vaska’s compound (example of oxidative
addition reaction- characteristic of organometallic))

H
L Cl L H
Ir + H2
Ir
OC L Cl L
CO

This reaction shows that oxidation state of Ir increases from

+1 to +3 and the oxidation number increases from 4 to 6.
 Carbonyl hydrides
The anionic hydrides like [HFe(CO)4]- are true hydrides and behave as reducing
agents for alkyl halides as shown below:

RX+ [HFe(CO)4]- → RH + [XFe(CO)4 ]-

 Carbonyl Halides
Reaction with halogens:
Most of the metal carbonyls react with halogens to give carbonyl
halides

Fe(CO)5 +X2 → Fe(CO)4X2 + CO (oxidative addition, increase in

oxidation state from 0 to +2 as well as coordination no.)

Mo(CO)6 + Cl2 → Mo(CO)4Cl2+2CO

Halogens can cause cleavage in the metal-metal bonds in case of

polynuclear carbonyls

Mn2(CO)10 +X2 → 2Mn(CO)5X

Some carbonyls undergo decomposition upon
reaction with halogens

Ni(CO)4 +Br2 → NiBr2 +4CO

Co2(CO)8 +2X2 → 2CoX2 +8CO

Methods of preparing carbonyl halides

4d65s2
Rhodium 4d7 5s2
Iridium 5d7 6s2
METAL METAL BONDING
Metal Metal bonding
Formation of a delta bond by the overlap of
two dxy orbitals
Ta3+ d2
a. They have short Re-Re distance of 2.20 A compared to Re-Re distance of 2.75
A in bulk metal.
b. B. They possess eclipsed conformation. Which is surprising. Since the sum of
the van der Waals radii of twp chlorine atoms is more than the experimentally
observed distance between the two chlorine atoms attached to two separate
Re ato, one would expect a less crowded staggered conformation to be more
stable.
The dx2-y2, s, px and py orbitals of each Re atom hybridise to give 4 dsp2 hybrid
orbitals on each Re atom. These hybrid orbitals accommodate 8 electrons donated
by four chloride ions attached to each Re.
The dz2 and pz orbitals of each Re atom hybridise to give two dp hybrid
orbitals on each Re atom. A dp orbital of one Re atom overlaps with
similar orbital on other Re atom to yiela sigma bonding and antibonding
orbitals. Each re atom is thus left with nonbonding hybrid orbital.
dxy in eclipsed form dxy in staggered form
 ISOLOBAL ANALOGIES

• Isolobal principle is a strategy used in organometallic chemistry

to relate the structure of organic and inorganic molecular
fragments in order to predict bonding properties of
organometallic compounds.
• According to the isolobal concept, if the two sets of frontier
orbitals belonging to two different molecular fragments are
same in number, symmetry and shapes, the two molecular
fragments are called isolobal fragments. The orbitals whose
similarity is important in determining the isolobality of the
molecular fragment are called frontier orbitals.
 ISOLOBAL ANALOGIES

• One can predict the bonding and reactivity of one of the less
known species from that of better known species if the two
molecular fragments have similar frontier orbitals i.e. HOMO
and LUMO.
• One can predict the bonding and reactivity of one of the
less known species from that of better known species if the
two molecular fragments have similar frontier orbitals i.e.
HOMO and LUMO.
 ISOLOBAL ANALOGIES

• The concept of isolobality is the outcome of the attempts to draw

an analogy between the Lewis octet rule applicable to main
group chemistry (specially organic chemistry) and the 18 e- rule
applicable to transition metal organometallic chemistry.
• The isolobal analogy allows to relate and compare organic,
inorganic and organometallic compounds on one uniform basis.
• What in common have
CH3, NH2, OH, F, Cl, Co(CO)4 and CpMo(CO)3 ?
• These “fragments” or “building blocks” can replace each other
in more complex structures. For example, all the groups above
can combine to form an ordinary bond:
• CH3-CH3, NH2-NH2, HO-OH, F-F, Cl-Cl, (CO)4Co-Co(CO)4,
CpMo(CO)3-Mo(CO)3Cp
 CH3-NH2, CH3-OH, CH3-F, CH3-Cl, CH3-Co(CO)4, CH3-Mo(CO)3Cp
NH2-OH, NH2-F, NH2-Cl, NH2-Co(CO)4, NH2-Mo(CO)3Cp etc.
“Fragments” or “building blocks” that can replace each other in
complex structures are isolobal.

• The definition: Two “fragments” are called isolobal if their

frontier orbitals: i) are same in number, ii) have similar
symmetry, iii) are of approximately the same energy, and iv)
have the same number of electrons on them.
• All examples above represent the case
of one singly occupied (SO) “working” HOMO
orbital:

CH3 Co(CO)4 a1
 Groups isolobal with CH3
• Electron-equivalent groups miss the same number of electrons necessary for
the central atom to reach the stable electronic configuration (8, 16, or 18 e’s,
etc.). Electron-equivalent groups are always isolobal.
HOMO
Isolobal # of e’s in the Stable electron # of missing e’s
groups valence shell configuration (“holes”)
CH3 4+3=7 8 1
NH2 5+2=7 8 1
OH 6+1=7 8 1
F 7 8 1 a1
Co(CO)4 9+4(2)=17 18 1
CpMoI(CO)3 5+6+3(2)=17 18 1

Transition metal derived fragments MLn isolobal with CH3

d1-ML8 d3-ML7 d5-ML6 d7-ML5 d9-ML4
(C8H8)2La Cp2V(CNR) CpMn(CO)3+ [Co(NH3)5]2+ Co(CO)4
 Groups isolobal with triplet CH2 (two SO
frontier orbitals)
• Groups that are electron-equivalent with the triplet methylene of (a1)1(b2)1
configuration have two electrons missing in the valence shell of the central
atom:
Isolobal # of e’s in the Stable electron # of missing e’s b2
groups valence shell configuration (“holes”)
CH2 4+2=6 8 2
NH 5+1=6 8 2 a1
O 6 8 2
Ni(CO)3 10+3(2)=16 18 2
Os(CO)4 8+4(2)=16 18 2
CpRh(CO) 6+8+2=16 18 2

• Combination of two fragments isolobal with CH2 gives “dimers” with double
bond between the fragments like in CH2=CH2: CH2=NH, CH2=O, CH2=Os(CO)4,
CpRh(CO)(=CH2) etc. (OC)CpRh
NH Fe(CO)4 RhCp(CO)
(OC)CpRh
(Fe ethylene complex)
 Groups isolobal with CH (three working SO frontier
orbitals)
• CH of (s)1(p)2 configuration is isolobal with N, O+, Co(CO)3, Re(CO)4, NiCp, CpW(CO)2 (and
W(OMe)3!) etc.
Group # of e’s in the Stable electron # of missing e’s
valence shell configuration
CH 4+1=5 8 3
N 5 8 3 
O+ 6-1=5 8 3
Co(CO)3 9+3(2)=15 18 3
Re(CO)4 7+4(2)=15 18 3 

CpWI(CO)2 5+6+ 2(2)=15 18 3

• Some combinations of the fragments above: CH≡N, CH≡O +, N≡O+, Cp(CO)2W≡WCp(CO)2

(CO)3
Ir P
Ir(CO)3 P
(OC)3Ir P (OC)4Co Co(CO)4 (OC)3Co Co(CO)3
Ir(CO)3 - 2CO
P
 5) Non-electron-equivalent isolobal groups
• CH3+ is isolobal with singlet CH2, Cr(CO)5, CpMn(CO)2, PtCl3-, Au(PPh3)+,
(all have one empty “working” orbital)
• All these species can react in the similar manner with donors of an electron
pair:
CH3+ + NH3  CH3-NH3+
Cr(CO)5 + NH3  H3N-Cr(CO)5
PtCl3- + NH3  H3N-PtCl3-
Au(PPh3)+ + NH3  H3N-Au(PPh3)+

More applications of the isolobal analogy:

• In boron cages isolobal groups can replace each other: BH, Si, Ge, Sn,
CH+, NH2+, Os(CO)3 etc. H
B 2-
H
C Sn 2-

HB BH HB BH Sn Sn
BH BH Sn

B C Sn
H H
 ISOLOBAL ANALOGIES

ORGANIC SPECIES
CH3 CH2 CH C
CH2- CH- CH2+ CH+
ORGANOMETALLIC FRAGMENTS
Co(CO)4 Fe(CO)4 Co(CO)3 Fe(CO)3
Mn(CO)5 Cr(CO)5 Mn(CO)4 Cr(CO)4
CpFe(CO)2 CpCo(CO) CpNi CpCo
CpCr(C0)3 CpMn(CO)2 CpFe(CO) CpMn(CO)
Ni(CO)3 CpCr(CO)2
D3h
 C2v D
3h

a double bond as shown in fig.

Polynuclear carbonyls

Td
C3v
 STRUCTURE OF HIGH NUCLEARITY CARBONYL CLUSTERS

These clusters contains five or more than five metal atoms directly
bonded to one another. A large number of such carbonyl clusters have
been recently isolated.

Examples are Rh6(CO)16, Ru6(CO)18H2 and {(Ni3(CO)6}n2-.

Many mixed carbonyl clusters containing encapsulated C atom known as

Carbido carbonyl clusters

Example are Fe5(CO)15C, Ru6C(CO)17,

Nitrido complex

[Ru6N(CO)16]-
Rh =45 4d75s2

Os =76 5d6 6s2

Ru= 44, 4d6 5s2