Bridging ligand

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An example of a m2 bridging ligand, represented with the red letter "L" Bridging ligand.svg
An example of a μ2 bridging ligand, represented with the red letter "L"

In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. [1] 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.

Contents

In naming a complex wherein a single atom bridges two metals, the bridging ligand is preceded by the Greek letter mu, μ, [2] with a subscript 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.

List of bridging ligands

Virtually all ligands are known to bridge, with the exception of amines and ammonia. [3] Common bridging ligands include most of the common anions.

Bridging ligandNameExample
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 bridging carbonyl
Cl chloride Nb2Cl10 , see halide ligands
H hydride B2H6
CN cyanide approx. Fe7(CN)18 (prussian blue), see cyanometalate
PPh2 diphenylphosphide see transition metal phosphido complexes

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

Bonding

For doubly bridging (μ2-) ligands, two limiting representation are 4-electron and 2-electron bonding interactions. These cases are illustrated in main group chemistry by [Me2Al(μ2-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 iron–iron bond by virtue of a 3-center 2-electron bond involving one of three bridging CO ligands. [5]

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

Bridge-terminal exchange

The interchange of bridging and terminal ligands is called bridge-terminal exchange. The process is invoked to explain the fluxional properties of metal carbonyl and metal isocyanide complexes. [6] Some complexes that exhibit this process are cobalt carbonyl and cyclopentadienyliron dicarbonyl dimer:

Co2(μ-CO)2(CO)6 Co2(μ-CO)2(CO)4(CO)2
(C5H5)2Fe2(μ-CO)2(CO)2 (C5H5)2Fe2(μ-CO)2(CO)2

These dynamic processes, which are degenerate, proceed via an intermediate where the CO ligands are all terminal, i.e. (CO)4Co−Co(CO)4 and (C5H5)(CO)2Fe−Fe(CO)2C5H5.

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 CO2−3 and the related carboxylates, PO3−4 , and the polyoxometalates. Several organophosphorus ligands have been developed that bridge pairs of metals, a well-known example being Ph2PCH2PPh2 .

See also

Related Research Articles

<span class="mw-page-title-main">Coordination complex</span> Molecule or ion containing ligands datively bonded to a central metallic atom

A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those that include transition metals, are coordination complexes.

<span class="mw-page-title-main">Inorganic chemistry</span> Field of chemistry

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<span class="mw-page-title-main">Ligand</span> Ion or molecule that binds to a central metal atom to form a coordination complex

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<span class="mw-page-title-main">Pi backbonding</span> Movement of electrons from one atoms orbital to a symmetric antibonding orbital on another

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A description of the bonding of π-conjugated ligands to a transition metal which involves a synergic process with donation of electrons from the filled π-orbital or lone electron pair orbital of the ligand into an empty orbital of the metal (donor–acceptor bond), together with release (back donation) of electrons from an nd orbital of the metal (which is of π-symmetry with respect to the metal–ligand axis) into the empty π*-antibonding orbital of the ligand.

<span class="mw-page-title-main">Iron pentacarbonyl</span> Chemical compound

Iron pentacarbonyl, also known as iron carbonyl, is the compound with formula Fe(CO)5. Under standard conditions Fe(CO)5 is a free-flowing, straw-colored liquid with a pungent odour. Older samples appear darker. This compound is a common precursor to diverse iron compounds, including many that are useful in small scale organic synthesis.

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<span class="mw-page-title-main">Metal carbonyl</span> Coordination complexes of transition metals with carbon monoxide ligands

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.

<span class="mw-page-title-main">Hapticity</span> Number of contiguous atoms in a ligand that bond to the central atom in a coordination complex

In coordination chemistry, hapticity is the coordination of a ligand to a metal center via an uninterrupted and contiguous series of atoms. The hapticity of a ligand is described with the Greek letter η ('eta'). For example, η2 describes a ligand that coordinates through 2 contiguous atoms. In general the η-notation only applies when multiple atoms are coordinated. In addition, if the ligand coordinates through multiple atoms that are not contiguous then this is considered denticity, and the κ-notation is used once again. When naming complexes care should be taken not to confuse η with μ ('mu'), which relates to bridging ligands.

<span class="mw-page-title-main">Triiron dodecacarbonyl</span> Chemical compound

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<span class="mw-page-title-main">Diiron nonacarbonyl</span> Chemical compound

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<span class="mw-page-title-main">Tungsten hexacarbonyl</span> Chemical compound

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tert-Butyl isocyanide is an organic compound with the formula Me3CNC (Me = methyl, CH3). It is an isocyanide, commonly called isonitrile or carbylamine, as defined by the functional group C≡N-R. tert-Butyl isocyanide, like most alkyl isocyanides, is a reactive colorless liquid with an extremely unpleasant odor. It forms stable complexes with transition metals and can insert into metal-carbon bonds.

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<span class="mw-page-title-main">Metal amides</span>

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<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl dimer</span> Chemical compound

Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).

A metal carbido complex is a coordination complex that contains a carbon atom as a ligand. They are analogous to metal nitrido complexes. Carbido complexes are a molecular subclass of carbides, which are prevalent in organometallic and inorganic chemistry. Carbido complexes represent models for intermediates in Fischer–Tropsch synthesis, olefin metathesis, and related catalytic industrial processes. Ruthenium-based carbido complexes are by far the most synthesized and characterized to date. Although, complexes containing chromium, gold, iron, nickel, molybdenum, osmium, rhenium, and tungsten cores are also known. Mixed-metal carbides are also known.

<span class="mw-page-title-main">Transition metal acyl complexes</span>

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References

  1. IUPAC , Compendium of Chemical Terminology , 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) " bridging ligand ". doi : 10.1351/goldbook.B00741
  2. International Union of Pure and Applied Chemistry (2005). Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005). Cambridge (UK): RSC IUPAC . ISBN   0-85404-438-8 . pp. 163–165. Electronic version.
  3. Werner, H. (2004). "The Way into the Bridge: A New Bonding Mode of Tertiary Phosphanes, Arsanes, and Stibanes". Angew. Chem. Int. Ed. 43 (8): 938–954. doi:10.1002/anie.200300627. PMID   14966876.
  4. Koo, H.-J.; Whangbo, M.; VerNooy, P. D.; Torardi, C. C.; Marshall, W. J. (2002). "Flux growth of vanadyl pyrophosphate, (VO)2P2O7, and spin dimer analysis of the spin exchange interactions of (VO)2P2O7 and vanadyl hydrogen phosphate, VO(HPO4).0.5H2O". Inorg. Chem. 41 (18): 4664–72. doi:10.1021/ic020249c. PMID   12206689.
  5. 1 2 Green, J. C.; Green, M. L. H.; Parkin, G. (2012). "The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds". Chem. Commun. 2012 (94): 11481–503. doi:10.1039/c2cc35304k. PMID   23047247.
  6. Adams, R. D.; Cotton, F. A. (1973). "Pathway of Bridge-Terminal Ligand Exchange in Some Binuclear Metal Carbonyls. Bis(pentahapto-cyclopentadienyldicarbonyliron) and Its Di(methyl Isocyanide) Derivative and Bis(pentahapto-cyclopentadienylcarbonylnitrosylmanganese)". Journal of the American Chemical Society. 95 (20): 6589–6594. doi:10.1021/ja00801a012.