ISOLOBAL ANALOGY

• The parallels between organic and inorganic compounds were first

described by Roald Hoffman
• The molecular fragments of a cluster are deemed to be isolobal if
they possess same number of frontier molecular orbitals with:
i) similar shape, symmetry and radial extent;
ii) approximately the same energy;
iii) same number of electrons available for cluster bonding.
• Some of the reactions of the metal carbonyls are parallel with
main group non-metals and compounds.
• Example
Electrons short of a Main Group Metal carbonyl Organic Group
filled shell

1 Cl Mn(CO)5 CH3
2 S Fe(CO)4 CH2
3 P Co(CO)3 CH
GENERATING ISOLOBAL FRAGMENTS
ISOLOBAL SCHEME
Isolobal analogy between metal complexes and organic moieties.
Extension of analogy
Isoelectronic relationships
Two atoms, ions, or molecules that have the same electronic structure and the
same number of valence electrons.

1) Species of the same or similar composition containing metals from the same
group are isoelectronic
Mn(CO)5/Re(CO)5
Co(CO)3/Ir(CO)3
CpMo(CO)3/CpW(CO)3
2) Species with same/similar ligands containing metal atoms from different
groups with suitable change in net charge are isoelectronic
Fe(CO)3-/Co(CO)3
3) Species in which NO is substituted for CO, with proper charge adjustment, if
necessary, are isoelectronic
NiNO/Co(CO)2
CpFe(NO)R/CpCo(CO)R
4) The replacement of one CO ligand by two electrons or two H atoms gives
isoelectronic species
Fe5C(CO)15/[Fe5C(CO)14]2-
[Re6C(CO)19]2-/[Re6C(CO)18H2]2-

5) A special case is based upon the fact that arene ligands such as C6H6 and C5H5- are six
electron donors, thus we have sets of isoelectronic species such as;
C6H6Cr/C5H5Mn/Cr(CO)3
C5H5Ni/C6H6Co