Metal Clusters

Metal Clusters
• A group of two or more metal atoms in which there are direct
or substantial bonds between metal atoms.
• No central atom
• Direct or indirect bonds between atoms forming cage like or
polyhedral structure.
• Polyhedral geometry like trigonal bipyramidal, tetrahedron,
octahedral etc.
Types Of Metal Clusters
• Polynuclear Carbonyl, Nitrosyl or related compounds
• When ligands are 𝐶 ≡ 𝑂 or N ≡ 𝑂
• Low valency type
• Metals atoms are in +1, 0 or -1 oxidation state
• Polynuclear Halides & Oxides
• When ligands are 𝐶𝑙− , 𝑂−−
• High valency type
• Metal atoms are in +2, +3, - - - - - oxidation state
Metal Carbonyls
• When carbon monoxide acts as an ligand
• Transition metal (Fe, Co, Ni) in zero valent state forms compound with
𝐶≡𝑂
• 𝐶 ≡ 𝑂 is a pi-acceptor ligand
• π-acid ligand
• Stabilize metals in zero valent state
Bonding

𝑪≡𝑶
• 2 types of orbital in CO
• Filled bonding orbital
• Vacant antibonding orbital
• σ bond is formed
• π acceptance is formed at vacant π antibonding orbital
• Metal to carbon σ bond is formed because electron density being
transferred from carbon to metal
• Carbon monoxide has vacant π antibonding orbital
• Antibonding π orbital is low energy
• Electron density from metal transfer to carbon monoxide and π bond
is formed
• Synergic bond is formed metal to carbon
18 Electron Rule
• Metal carbonyl follows 18 electron rule
• Total number of electron in outer shell of metal and electron donated
by CO equals 18 electrons
• For example, 𝐹𝑒(𝐶𝑂)5
• Fe = 8
• Electron from CO = 5 x 2 = 10
• Total electron = 10 + 8 = 18
Structure Of Di Nuclear Carbonyl
• There is direct M-M bond and each metal is bonded to terminal
carbonyl group by co-ordinate bond
• Eg. 𝑀𝑛2 (𝐶𝑂)10 , 𝑇𝑐2 (𝐶𝑂)10 , 𝑅𝑒2 (𝐶𝑂)10
• Mn(0) = 3𝑑 5 4𝑠 2 = 7
• 5CO = 5 x 2 = 10
1ē
• 1 M-M bond =
18ē
• It is a diamagnetic
• 𝐷4𝑑 symmetry
Type 2
• When both terminal bridging carbonyl
groups present
• Bridging carbonyl attach to metal by
• Terminal carbonyl 𝑀 ← 𝐶 ≡ 𝑂
• M-M bonds are present so they are
diamagnetic
• Example, 𝐶𝑜2 (𝐶𝑂)8 , 𝐹𝑒2 (𝐶𝑂)9 , 𝑂𝑠2 (𝐶𝑂)9
• 𝐶𝑜2 (𝐶𝑂)8
Tri Nuclear Carbonyls
• There is a direct bond between three metal atoms
• Each metal atom is bonded to terminal carbonyl groups or bridging
carbonyl groups
• Example, 𝐹𝑒3 (𝐶𝑂)12 , 𝑅𝑢3 (𝐶𝑂)12 , 𝑂𝑠3 (𝐶𝑂)12
• 𝐹𝑒3 (𝐶𝑂)12 𝑀3 (𝐶𝑂)12
Poly Nuclear Carbonyl
• 𝑀4 (𝐶𝑂)12 , 𝑀6 (𝐶𝑂)16
Wade-Mingo’s Rule
• To determine the geometry of transition metal cluster compounds
• The number of electron is used to find the geometry of polyhedral
• Applicable to metal cluster
• Mingo extended this rule for transition metal cluster
Types Of Metal Cluster
• 𝑛 + 1 → 𝑐𝑙𝑜𝑠𝑜
• 𝑛 + 2 → 𝑛𝑖𝑑𝑜
• 𝑛 + 3 → 𝑎𝑟𝑎𝑐ℎ𝑛𝑜
• Where, 𝑛 = number of metal atoms
𝑇𝐸𝐶 −12×𝑛
• Skeletal electron pair (S) =
2
• Number of vertices of polyhedral = S - 1
Number of vertex Polyhedron
4 Tetrahedron
5 Trigonal Bipyramid
6 Octahedron
7 Pentagonal Bipyramid
8 (Trigonal) Dodecahedron
9 Tricapped Triagonal prism
10 Bicapped Square antiprism
11 Octadecadron
12 Icosahedron
• Example 1. 𝑅ℎ6 (𝐶𝑂)16
➢ Rh = 9

➢ TEC = 6 x 9 + 16 x 2 = 86

𝑇𝐸𝐶 −12 × 𝑛 86 −12 × 6 14

➢ S= = = =7
2 2 2

➢ To find n+1 or n+2 or n+3

➢ n+1=6+1=7 Closo structure

➢ Vertex = S – 1 = 7 – 1 = 6 (so polyhedron → octahedron)

➢ So it is Closo octahedron
• Example 2. 𝑂𝑠5 (𝐶𝑂)16
➢ Os = 8

➢ TEC = 5 x 8 + 16 x 2 = 72

𝑇𝐸𝐶 −12 × 𝑛 72 −12 × 5 12

➢ S= = = =6
2 2 2

➢ To find n+1 or n+2 or n+3

➢ n+1=5+1=6 Closo structure

➢ Vertex = S – 1 = 6 – 1 = 5

➢ So it is Closo trigonal bipyramid

• Example 3. 𝑂𝑠5 (𝐶𝑂)15 𝐶
➢ Os = 8

➢ TEC = 5 x 8 + 15 x 2 + 4 = 74

𝑇𝐸𝐶 −12 × 𝑛 74 −12 × 5 14

➢ S= = = =7
2 2 2

➢ To find n+1 or n+2 or n+3

➢ n+2=5+2=7 Nido structure

➢ Vertex = S – 1 = 7 – 1 = 6 (octahedron)

➢ So it is Nido octahedron
 2−
• Example 4. [𝐹𝑒4 𝐶 𝐶𝑂 12 ]
➢ TEC = 4 x 8 + 4 + 12 x 2 + 2 = 62

𝑇𝐸𝐶 −12 × 𝑛 74 −12 × 5 14

➢ S= = = =7
2 2 2

➢ To find n+1 or n+2 or n+3

➢ n+3=4+3=7 Arachno structure

➢ Vertex = S – 1 = 7 – 1 = 6 (octahedron)

➢ So it is Arachno octahedron
 −
• Example 5. [𝑅𝑢5 𝑁 𝐶𝑂 14 ]
➢ TEC = 5 x 8 + 5 + 1 + 14 x 2 = 74

𝑇𝐸𝐶 −12 × 𝑛 74 −12 × 5 14

➢ S= = = =7
2 2 2

➢ To find n+1 or n+2 or n+3

➢ n+2=5+2=7 Nido structure

➢ Vertex = S – 1 = 7 – 1 = 6 (octahedron)

➢ So it is Nido octahedron
Thank You