M-M bonds and Cluster chemistry

Definition: "a finite group of metal atoms that are held together
mainly, or at least to a significant extent, by bonds directly
between metal atoms, even though some non-metal atoms may
also be intimately associated with the cluster" – F.A. Cotton

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Two extreme types of metal clusters:

• Molecular clusters are composed of 3 or more metal atoms

stabilized by small molecules acting as ligands, and characterized
by metal-metal bonds, either localized or delocalized over the
metal framework.

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•"Naked clusters" - have no ligands, electronically unsaturated,
naked metal particles formed in atomic beams; are extremely
reactive unless stabilized by a support or an inert matrix, e.g.
[Pb5]2-.
In this part of the course, we focus on transition metal clusters
with 2 or more M-M bonds, and, particularly, late TM clusters
with CO ligands.

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Importance:

(a)

Evolution of properties as cluster size increases (e.g. structure,

magnetic behaviour, ionization potential):

Transition from molecular → bulk metal domain.

• metal-ligand charge transfer interactions are limited to the metal

atoms which are at the surface of the metal cluster; inner-core
metal atoms behave as a metal particle.
• properties of a solid gradually evolve as atoms are brought
together to form increasingly larger units. 4
(b)

Interpretation of data obtained from metal surfaces which

are active heterogeneous catalysis sites (cluster-surface analogy).

• models for chemi- and physi-sorption of small molecules onto

metallic surfaces - e.g. fluxionality of the coordinated fragments,
mechanism of hydrogen diffusion inside a metallic network, the
distortions in metal close-packing induced by interstitial
heteroatoms, etc.

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• chemical reactivity of coordinated ligands in molecular
metal clusters has been used for studying the reaction
mechanisms at the metal centres, and for mimicking
elementary processes relevant to homogeneous and
heterogeneous catalysts.

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c) Fascinating structures (!).

• first reports of organometallic transition metal clusters:

Fe2(CO)9 (1905), Fe3(CO)12 (1907) and Co2(CO)8 (1910)

• computer analysis of X-ray crystallographic data →

novel structural features

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• variety of metal frame shapes, bonding modes for any given
ligand and stereochemistry observed was only possible in the
presence of several metal atoms

• solid state chemists and physicists also became interested –

clusters as particulate metals enclosed in a ligand sphere.

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• 1000s of examples of ligated metal clusters have been reported.
Most common clusters are formed by:

-early transition metals stabilized by halide or oxygen atoms

(aggregates)

-metals of group 6-10 stabilized by CO molecules

- transition or post-transition metals having halogen atoms,

phosphine groups, and main group elements as ligands

• primary analytical tool is X-ray diffraction, bond lengths which

are shorter than the sum of the covalent radii being a reliable
indication of M-M bonding. 10
• one of the first reported X-ray structural determinations of
TMCCs was of Fe2(CO)9 (1939), revealed CO ligands bridging the
M-M bond.

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• historically, first unsupported M–M bonds were found in the
analogous complexes Re2(CO)10 and Mn2(CO)10 (1957). Confirmed
the existence of unsupported M-M bonds.

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• also very early on, the structure of the pentacoordinate
Fe5(μ5-C)(CO)15 (1962) and [Re2Cl8]2- .

• Interesting structures stimulated research; lack of syntheses

frustrated research. Recent systematic syntheses have led to the
explosion in cluster chemistry. 13
STRUCTURE AND BONDING

(1)TYPES OF CLUSTERS

(i) π-Donor clusters: early transition metals (oxidation

state +2 or +3) with π-donor ligands (O2–, S2–, Cl–, Br–, I–,
OR–, etc.). Typically triangular or octahedral geometries.

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Electron donating characteristics of common π-donor bridging
ligands

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Examples:

[Nb6Cl12]2+, [Ta6Cl12]2+ octahedral M6, edge-bridging Cl (1)

[Mo6Cl8]4+, [W6Cl8]4+ octahedral M6, face-capping Cl (2)

[Re3Cl12]3- triangular Re3, 3 x μ-Cl, 9 x terminal Cl (3)

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• COs frequency as a ligand for stabilizing low oxidation state
clusters arises because of its flexibility - coordination as terminal, μ-
and μ3- are all common and, because they are all 2e donors (unlike
Cl), intramolecular exchange processes frequently have very low
activation energies.

• H- is not a π-acceptor ligand, but there are many carbonyl clusters

that also have H- as a ligand, so these clusters are usually considered
together.

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Ligand bonding modes

• see more extensive discussion on bonding modes of CO, hydrido

and acetylenic ligands (later in course).

• Cl ligand is a 1 e donor when terminal, or uses a lone pair to

become a 3e donor when edge-bridging, or a 5e donor using an
additional lone pair when face bridging.

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Bonding modes and
electron count for some
common ligands

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(2) CLUSTER GEOMETRY –

• high symmetry - usually define regular polyhedra as triangle,

tetrahedra, octahedra, etc

• metal positions usually define deltahedra, i.e. Triangular faces;

other arrangements, e.g. square-planar, trigonal prismatic, square
antiprisms occur to lesser extent

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• many represent fragments of close-packed arrays of
metal atoms, hcp ccp or bcc

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• form interstitial complexes containing hydrogen,
carbon, nitrogen, sulfur, phosphorus, and arsenic, as well
as other metal atoms in the case of high-nuclearity
clusters, in the interstices

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3 metal atom clusters

• great majority are triangular. Structural differences

require only small changes in total energies of
molecules e.g. Fe3(μ-CO)2(CO)10 and Ru3(CO)12.

• linear e.g [Mn3(CO)14]- or bent. Bond opening

on a triangular cluster results in a linear geometry
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4 metal atom clusters:

• many are tetrahedral with 6 M–M bonds, e.g. CpWIr3(CO)11

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• butterflies can be regarded as resulting from a bond
opening on the tetrahedron

e.g. CpWIr3(CO)8(F3CC≡CCF3)2

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• interplanar angle in butterflies can be near 180°, as in
[Re4(CO)16]2-

• Fe4(μ4-C)(μ-CO)(CO)12 contains a carbide atom in the middle

of the cluster, approximately colinear with the wing-tip atoms,
providing an excellent model for a carbon atom on a metal
surface.

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• square-planar geometries - for carbonyl clusters, often
contain a capping ligand

e.g. Fe4(μ4-NEt)(μ3-η2-ONEt)(μ-CO)3(CO)8

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• bond rupture in a butterfly arrangement leads to a
spiked triangle geometry, as in Re4(μ-H)3H(CO)15

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Examples of preparations

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Ouch!

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n+1
n+1

n+1
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Os6(CO)18
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 EAN PSPET

n= 3 18x3 = 54-6 = 48 48-(12x3) = 12  6 pairs (arachno)

4 18x4 = 72-12 = 60 60- (12x4) = 12 6 pairs (nido)

5 18x5 = 90 – 18 = 72 72-(12x5) = 12  6 pairs (closo)

6 18x6 = 108 -24 = 84 n+2

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CHEM 3032 – Cluster Chemistry

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