METAL-METAL BONDS

• A bond between two metal centers

• Ranges from a single to a quadruple bond.

• The existence of metal-metal bond is mainly because of the presence of

(n+1)s, (n+1)p and nd orbitals as valence shell electronic configuration.
• The transition metals can form three general types of bonds such as covalent
bonds, dative bonds and weak metal-metal symmetry interactions where
covalent bonds being the strongest and symmetry interactions are the weakest.

COVALENT BONDING
This is the most common type of metal-metal bond ranging from a single to a
quadruple metal-metal bond. One electron from each metal atom constitutes a
single M-M bond between the two metal atoms.
Dative Bond:
• This type of bond is formed when one metal having filled d-orbitals coordinate
to a metal atom containing empty d-orbitals by the donation of a lone pair of
electron.
• Represented by an arrow, starting from the donor metal and pointing to the
unsaturated metal atom.
• Example: The bimetallic Ni complex has one dative bond.
Weak metal-metal symmetry interactions:
• A result of symmetrical overlap of molecular orbital. This overlap is
generally between filled and empty metal-metal bonding and/or anti-bonding
orbitals.
• Example, the Ir tetrakis(isocyanide) complexes form oligomeric chains
through M-M interacted stacks in solution and in the solid state without
showing any evidence of a metal-metal covalent bond
Molecular orbital theory
• Used to explain the overlap of various orbital to form three types of bonds
namely the σ-bond, π-bond and the δ-bond or the quadruple bond.

• A σ-bond between two metal atoms is a result of overlap of dz2 orbital from
each atom.
• Two π-bonds can be formed by the overlap of the dzx and dyz orbitals.
• Two δ-bonds can arise from the two face-to-face overlap of dxy and dx2‒y2
orbitals.

• The dx2‒y2 orbital is also utilized for bonding with ligands.

The energy diagram - the possibility of a quintuple bond which could result
when all the bonding orbitals are occupied to give an electronic
configuration of σ2π4δ4.
➢ π-overlap is smaller than σ-overlap,
therefore the split in energy between the
bonding and the anti-bonding π-orbitals is
smaller than the split between the bonding
and the anti-bonding σ-orbitals

➢ The δ-overlap is even smaller than the π-

overlap, therefore the energy split between
the bonding and the anti-bonding δ-orbitals
is even smaller than those for the π and π*-
orbitals.
So what would be the maximum bond order that
could be achieved?
• The maximum bond order would be achieved when all bonding MOs were
full, and all anti-bonding MOs were empty.
• We have overall five bonding MOs that we could fill with ten electrons from
two metal atoms with d5-electron configuration.
• The maximum bond order, BO =5.
• In practice only bond orders up to 4 are well known. This is because the dx2-
y2 orbital is usually too involved in the bonding with the ligands thereby
becoming unavailable for metal-metal interactions.
Relationship between metal-metal bond order and electron
configuration

• The bond order increases from 1 to 4 with the electron configuration

changing from d1 to d4.

• At d4 all bonding MOs are full with eight electrons.

Example of a complex with a bond order of 4: tetraacetatodiaquadichromium
complex

➢ Cr is in the oxidation state +2, which makes the

chromium a d4 species.

Counting the valence electrons.

✓ A neutral Cr atom has 6 VE, and an electron

configuration 3d54s1.
✓ Four acetate ligands having a -1 charge each which
gives four negative charges overall.
✓ The complex is overall neutral; each Cr must have
formally a 2+ charge, and the electron configuration
is 3d4.
Predict the bond order of the following complexes
What experimental evidence exists for the presence
of metal-metal multiple bonds?
Bond length

The shorter the bond, the higher the bond order.

Conformation of a molecule

The rhenium is in the oxidation state +3, thus it is a d4 species, and we would
argue that there may be a Re-Re quadruple bond. This quadruple bond can only
form when the dxy orbitals are in eclipsed conformation, and this is only possible
when the two ReMe4 fragments are in eclipsed conformation.