Bridging ligand

File:Bridgingligand.png

An example of a μ² bridging ligand

A bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually restricted to small ligands such as pseudohalides or to ligands that are specifically designed to link two metals.

In naming a complex wherein a single atom bridges two metals, the bridging ligand is preceded by the Greek character 'mu', μ, with a superscript number denoting the number of metals bound to the bridging ligand. μ² is often denoted simply as μ. When describing coordination complexes care should be taken not to confuse μ with η ('eta'), which relates to hapticity. Ligands that are not bridging, are called terminal ligands (see figure).

List of bridging inorganic ligands

Virtually all ligands are known to bridge, with the exception of amines and ammonia. Common inorganic bridging ligands include most of the common anions.

bridging ligand	name	example
OH−	hydroxide	[Fe2(OH)2(H2O)8]4+, see olation
O2−	oxide	[Cr2O7]2−, see polyoxometalate
SH−	hydrosulfido	Cp2Mo2(SH)2S2
NH2−	amido	HgNH2Cl
N3−	nitride	[Ir3N(SO4)6(H2O)3]4−, see metal nitrido complex
CO	carbonyl	Fe2(CO)9, see metal carbonyl#Bridging carbonyls
Cl−	Chloride	Nb2Cl10, see metal halide#Halide ligands
H−	Hydride	B2H6
CN−	Cyanide	approx. Fe7(CN)18, see cyanometalate

Many simple organic ligands form strong bridges between metal centers. Many common examples include organic derivatives of the above inorganic ligands (R = alkyl, aryl): OR⁻, SR⁻, NR₂⁻, NR²⁻ (imido), PR₂⁻ (phosphido, note the ambiguity with the preceding entry), PR²⁻ (phosphinidino), and many more.

Examples

• Compounds and Complexes with Bridging Ligands
• Mu-Cl.png

  In this ruthenium complex ((benzene)ruthenium dichloride dimer), two chloride ligands are terminal and two are μ² bridging.

• Creutz-Taube-Ion.svg

  Pyrazine is a bridging ligand in this diruthenium compounds, called the Creutz-Taube complex.

• Mu3 compound.png

  In the cobalt cluster Co₃(CO)₉)Ct-Bu), the Ct-Bu ligand is triply bridging, although this aspect is typically not indicated in the formula.

• Fe3(CO)12lessFe-Fe.png

  In triiron dodecarbonyl, two CO ligands are bridging and ten are terminal ligands. The terminal and bridging CO ligands interchange rapidly.

• Niobium-pentachloride-dimer-2D.png

  In NbCl₅, there are two bridging and eight terminal chloride ligands.

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  The cluster [Au₆C(PPh₃)₆]²⁺ features μ⁶-carbide ligand, although again, the designator "μ" is not usually used.

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  In rhenium trioxide, the oxide ligands are all μ². These oxide ligands "glue" together the metal centres.

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  In the case of ZrCl₄, there are both terminal and doubly bridging chloride ligands.

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  In rhodium(II) acetate, the four acetate groups are bridging ligands.

Bonding

For doubly bridging (μ²-) ligands, two limiting representation are 4e and 2e bonding interactions. These cases are illustrated in main group chemistry by [Me₂Alμ²-Cl]2 and [Me₂Al(μ²-Me)]₂. Complicating this analysis is the possibility of metal-metal bonding. Computational studies suggest that metal-metal bonding is absent in many compounds where the metals are separated by bridging ligands. For example, calculations suggest that Fe₂(CO)₉ lacks an Fe-Fe bond by virtue of a 3-center 2-electron bond involving one of three bridging CO ligands.

File:BridgingLs.png

Representations of two kinds of M-bridging ligand interactions, 3-center, 4 electron bond (left) and 3-center, 2 electron bonding.

Polyfunctional ligands

Polyfunctional ligands can attach to metals in many ways and thus can bridge metals in diverse ways, including sharing of one atom or using several atoms. Examples of such polyatomic ligands are the oxoanions CO₃²⁻ and the related carboxylates, PO₄³⁻, and the polyoxometalates. Several organophosphorus ligands have been developed that bridge pairs of metals, a well-known example being Ph₂PCH₂PPh₂.

See also

• Bridging carbonyl