PRESENTATION ON

ISOLOBAL
ANALOGY
PRESENTED BY
KUNDAN KUMAR OJHA
ROLL NO. – 204120011
M.Sc. 2ND SEM.
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 INTRODUCTI
ON
The problem we have in organometallic chemistry or even inorganic chemistry
is the fact that we do not have the same systemisation, that is available in
organic chemistry. So, a concept of isolobal analogy was introduced by Nobel
lauerate Roald Hoffmann in 1981. The isolobal analogy allows us to relate and
compare organic, inorganic & organometallic compounds on one uniform basis.

Hoffmann described molecular fragments as isolobal,

if the number, symmetry properties, approximate energy and shape of the

frontier orbitals and the number of electrons in them are similar.

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 ISOLOBAL ANALOGY

• Considering fragments of methane and an octahedral complex.

• The parent compounds have filled valence-shell electron configurations,

eight electrons (octet) for CH4 and 18 electrons for ML6.

• Methane is considered to use sp3 hybrid orbitals in bonding, with eight

electrons occupying bonding orbitals formed from interactions between
the hybrid orbital and 1s orbitals on the hydrogens.

• The metal in ML6 uses d2sp3 hybrids to bond to the ligands, with 12
electrons occupying bonding orbitals and six nonbonding electrons
occupying dxy, dxz, and dyz orbitals.

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 ISOLOBAL aNALOGY
.

Orbitals of Parent Structures CH4 and ML6

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 ISOLOBAL ANALOGY

• For the purpose of the analogy, these fragments are

assumed to preserve the original geometry of the
remaining ligands.

• Tetrahedral CH4 and octahedral ML6 can form 7- and

17- electron fragment.

• To form the fragments, the C–H and M–L bonds are

assumed to cleave homolytically.

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 ISOLOBAL ANALOGY
 Each of these fragments has a single electron in a hybrid orbital at the vacant
site of the parent polyhedron.

 These orbitals are sufficiently similar to meet Hoffmann’s isolobal definition.

 Using Hoffmann’s symbol to designate groups as isolobal, we may therefore

write the following.

CH3 Mn(CO)5

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 ISOLOBAL ANALOGY 7

• Similarly, 6-electron CH2 and 16-electron ML4 are isolobal.

• Each of these fragments represents the parent polyhedron, with single electrons occupying
two hybrid orbitals at otherwise vacant sites.

• Each fragment also has two electrons fewer than the filled shell octet or 18-electron
configurations.
 ISOLOBAL FRAGMNENTS
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• Correlation between transition element & main group fragments according

to electron count
S.No. Transition element/fragmnent Main group element/fragmnent
1 18 8
2 17 7
3 16 6
4 15 5
5 14 4
 Similarities between fragmnets
• Isolobal fragments can be formally combined into molecules.

For example, two CH3 fragments, when linked, form ethane, and two Mn(CO)5 fragments
form the dimeric (OC)5Mn–Mn(CO)5.

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 Similarities between fragmnets

• Furthermore, organic and organometallic fragments can also be intermixed.

E.g. H3C–Mn(CO)5 is also a known compound.

• Organic and organometallic parallels are not always this complete.

For example, whereas two 6-electron CH2 fragments form ethylene, H2C=CH2, the
dimer of the isolobal Fe(CO)4 is not nearly as stable.
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Extension of Analogy

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 Extension of Analogy

• Analogies are not only limited to organometallic fragments of octahedra.

• Similar arguments can be used to derive fragments of different polyhedra.

For example, Co(CO)4, a 17-electron fragment of a trigonal bipyramid, is isolobal with Mn(CO) 5,

a 17-electron fragment of an octahedron.

• The compound composed of these two fragments, (CO)5Mn—Co(CO)4, is known.

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Isolobal Relationships for Fragments of Polyhedra

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 APPLICATION 14

• A practical use of isolobal analogies is in suggesting

syntheses of new compounds.

• For example, CH2 is isolobal with 16-electron Cu(η5 –Cp)

and with 14-electron PtL2 (L = PR3, CO).

• All three of these fragments are two ligands and two

electrons short of their parent polyhedra.

• Recognition that these fragments are isolobal has been

exploited in preparing new organometallic compounds
composed of fragments isolobal with fragments of known
compounds
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