The Organometallic Reader

Dedicated to the teaching and learning of modern organometallic chemistry.

Epic Ligand Survey: π Systems (Part 2)

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Epic Ligand Survey: Pi Systems (Part 2)Arene or aromatic ligands are the subject of this post, the second in our series on π-system ligands. Arenes are dative, L-type ligands that may serve either as actors or spectators. Arenes commonly bind to metals through more than two atoms, although η2-arene ligands are known. Structurally, most η6-arenes tend to remain planar after binding to metals. Both “normal” bonding and backbonding are possible for arene ligands; however, arenes are stronger electron donors than CO and backbonding is less important for these ligands. The reactivity of arenes changes dramatically upon metal binding, along lines that we would expect for strongly electron-donating ligands. After coordinating to a transition metal, the arene usually becomes a better electrophile (particularly when the metal is electron poor). Thus, metal coordination can enable otherwise difficult nucleophilic aromatic substitution reactions.

General Properties

The coordination of an aromatic compound to a metal center through its aromatic π MOs removes electron density from the ring. I’m going to forego an in-depth orbital analysis in this post, because it’s honestly not very useful (and overly complex) for arene ligands. π → dσ (normal bonding) and dπ → π* (backbonding) orbital interactions are possible for arene ligands, with the former being much more important, typically. To simplify drawings, you often see chemists draw “toilet-bowl” arenes involving a circle and single central line to represent the π → dσ orbital interaction. Despite the single line, it is often useful to think about arenes as L3-type ligands. For instance, we think of η6-arenes as six-electron donors.

Multiple coordination modes are possible for arene ligands. When all six atoms of a benzene ring are bound to the metal (η6-mode), the ring is flat and C–C bond lengths are slightly longer than those in the free arene. The ring is bent and non-aromatic in η4-mode, so that the four atoms bound to the metal are coplanar while the other π bond is out of the plane. η4-Arene ligands show up in both stable complexes (see the figure below) and reactive intermediates that possess an open coordination site. To generate the latter, the corresponding η6-arene ligand undergoes ring slippage—one of the π bonds “slips” off of the metal to create an open coordination site. We’ll see ring slippage again in discussions of the aromatic cyclopentadienyl and indenyl ligands.

Arene ligands exhibit multiple coordination modes.

Arene ligands exhibit multiple coordination modes.

Even η2-arene ligands bound through one double bond are known. Coordination of one π bond results in dearomatization and makes η2-benzene behave more like butadiene, and furan act more like a vinyl ether. With naphthalene as ligand, there are multiple η2 isomers that could form; the isomer observed is the one that retains aromaticity in the free portion of the ligand. In fact, this result is general for polycyclic aromatic hydrocarbons: binding maximizes aromaticity in the free portion of the ligand. In the linked reference, the authors even observed the coordination of two different rhodium centers to naphthalene—a bridging arene ligand! Other bridging modes include σ, π-binding (the arene is an LX-type ligand, and one C–M bond is covalent, not dative) and L2-type bridging through two distinct π systems (as in biphenyl).

Arene ligands are usually hydrocarbons, not heterocycles. Why? Aromatic heterocycles, such as pyridine, more commonly bind using their basic lone pairs. That said, a few heterocycles form important π complexes. Thiophene is perhaps the most heavily studied, as the desulfurization of thiophene from fossil fuels is an industrially useful process.

Synthesis

There are two common methods for the stoichiometric synthesis of arene “sandwich” complexes, in which a metal is squished between two arenes. Starting from a metal halide, treatment with a Lewis acid and mild reductant rips off the halogen atoms and replaces them with arene ligands. The scope of this method is fairly broad metal-wise.

The Fischer-Hafner synthesis. Reduction of metal halides in the presence of arene.

The Fischer-Hafner synthesis. Reduction of metal halides in the presence of arene.

A second method, “co-condensation,” involves the simultaneous condensation of metal atom and arene vapor onto a cold (-196 °C) surface.

Syntheses of metal arene carbonyl complexes take advantage of the fact that arenes are strongly binding, “chelating” ligands. Infrared spectroscopic studies have shown that a single benzene ligand is a stronger electron donor than three CO ligands—C–O stretching frequencies are lower in metal arene carbonyls than homoleptic metal carbonyls. Since the process is entropically driven, a little heat can get the job done.

Entropically driven synthesis of arene complexes: three molecules for the price of one!

Entropically driven synthesis of arene complexes: three molecules for the price of one!

Reactions

It’s important here to distinguish aromatic X-type ligands from the topic of this post, Ln-type arenes bound only through their π systems. The figure below nicely summarizes the typical behavior of arene ligands coordinated through their π clouds. Although the figure is for chromium carbonyls specifically, other metals apply as well. Note the reactivity of the benzylic position: both cations and anions are stabilized by the metal.

The magic of metal coordination: increased acidity and electrophilicity and steric hindrance.

The magic of metal coordination: increased acidity and electrophilicity and steric hindrance.

Since the coordination of arenes to metals depletes electron density on the arene, it makes sense that metal-arene complexes should be susceptible to nucleophilic aromatic substitution (NAS). In fact, NAS on metal-coordinated arene ligands has been extensively developed for several different metals. However, all of these NAS methods are stoichiometric because the product ligands are as good as (or better than) the starting ligands at coordinating metal. A stoichiometric amount of another reagent—typically an oxidant—is used to free up the arene. Why are oxidants effective at freeing arene ligands from metal centers? Oxidation worsens the metal’s ability to backbond and consequently decreases the enthalpic advantage of arene binding. Entropy is thus able to take over and release the ligand.

Steric hindrance on the side of the arene bound to the metal is a second important factor to consider. Nucleophilic addition takes place on the face opposite the coordinated metal. If rearomatization through the loss of a leaving group isn’t fast, an electrophile can be introduced after nucleophilic addition, resulting in the cis addition of nucleophile and electrophile across an aromatic π bond. Take that, aromaticity!

Aromaticity takes a beating, thanks to chromium!

Aromaticity takes a beating, thanks to chromium!

We already touched a little on the interesting behavior of η2-arene complexes, which behave more like their analogues possessing one less double bond. Here’s a nifty example from Harman of a Diels-Alder reaction in which a substituted styrene is the diene. Strike two for aromaticity!

Harman's Os(II) arene chemistry. Styrene is uniquely acting like a diene!

Harman's Os(II) arene chemistry. Styrene is uniquely acting like a diene!

If you’re interested in learning more about this fascinating chemistry, check out Harman’s review (linked above). The behavior of furan is particularly intriguing.

This brings us to the end of our short series on L-type π-system ligands. However, we’ll encounter ligands that bear great similarity to alkenes and arenes in the near future. π Systems that contain an odd number of atoms, unlike π systems we’ve seen so far, are LnX-type ligands with one covalent M–X bond and n dative bonds. We’ll return to this interesting class of ligands after finishing off the dative ligands with metal carbenes and introducing a few simple X-type ligands (hydrides, alkyls, alkoxides, etc.). Don’t touch that dial!

6 Responses

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  1. Funny story about Dean Harman: while I was doing research for this post, I came across his group’s website…

    http://faculty.virginia.edu/harman1/index.shtml

    I couldn’t shake the feeling that I had seen this guy give a talk somewhere. A few minutes later, it hit me…

    Harman’s videos were associated with my general chemistry textbook in 2004. Feels like ancient history now, but I think my personal chemical education has come full circle!😛

    mevans86

    February 2, 2012 at 10:52 pm

  2. A quick note on the “η” (eta) system: ηn refers to the number of contiguous atoms in a π-system ligand bound to the metal. Alkenes are thus η2 ligands and fully engaged benzenes are η6. Here’s the IUPAC Gold Book’s characteristically verbose definition:

    “An affix giving a topological indication of the bonding between a π-electron ligand and the central atom in a coordination entity. A right superscript numerical index indicates the number of ligating atoms in the π-electron system of the ligand which bind to the central atom.”

    Source: http://goldbook.iupac.org/H01881.html

    mevans86

    February 2, 2012 at 11:11 pm

  3. another homerun. maybe it’s bc I gained experience and perspective, but I bet my grad school inorganic for organikers class would have gone a lot more smoothly with this blog in my back pocket.

    azmanam

    February 3, 2012 at 7:29 am

    • I must warn you, my good man, I am susceptible to flattery.😛

      This is only the tip of the iceberg! Just wait until we start discussing reactivity in detail…

      mevans86

      February 3, 2012 at 2:02 pm

  4. will alkynes be included in these later discussions?

    amf

    February 5, 2012 at 2:29 am

    • Most definitely! After the “Epic Ligand Survey” is done, I plan to revisit more specific ligands within each general class. Alkynes will be included there for sure.

      mevans86

      February 8, 2012 at 9:40 am


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