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Metal Clusters

Metal clusters are groups of two or more metal atoms that are directly or substantially bonded together. They form cage-like or polyhedral structures without a central atom. Metal clusters include polynuclear carbonyl, nitrosyl, and halide compounds. Carbonyl clusters feature transition metals in the zero oxidation state bonded to carbon monoxide ligands. They obey the 18 electron rule and often have di-, tri-, or poly-nuclear structures. The geometry of transition metal clusters can be determined using Wade-Mingo's rule based on the total electron count.

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2K views23 pages

Metal Clusters

Metal clusters are groups of two or more metal atoms that are directly or substantially bonded together. They form cage-like or polyhedral structures without a central atom. Metal clusters include polynuclear carbonyl, nitrosyl, and halide compounds. Carbonyl clusters feature transition metals in the zero oxidation state bonded to carbon monoxide ligands. They obey the 18 electron rule and often have di-, tri-, or poly-nuclear structures. The geometry of transition metal clusters can be determined using Wade-Mingo's rule based on the total electron count.

Uploaded by

Syed Safi Ahmed
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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

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