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Chemistry LibreTexts

Organometallic Ligands

  • Page ID
    711
  • [ "article:topic-guide", "showtoc:no", "authorname:mevans", "Organometallic Ligands" ]

    • Carbenes
      Fischer carbenes, Shrock carbenes, and vinylidenes are usually actor ligands, but they may be either nucleophilic or electrophilic, depending on the nature of the R groups and metal. In addition, these ligands present some interesting synthetic problems: because free carbenes are quite unstable, ligand substitution does not cut the mustard for metal carbene synthesis.
    • Dative Ligands of N, O, and S
      L-type ligands of nitrogen, oxygen, and sulfur are important for at least two reasons: (1) coordination to a metal can modify the reactivity of the bound functional group, and (2) dative coordination is a critical element of organometallic reactions that depend on intramolecular directing group effects. “Long-term” ligands containing two-connected nitrogens, such as pyridines and oxazolines, are now among the most commonly used for organometallic reactions.
    • Metal Alkyls
      Metal alkyls feature a metal-carbon σ bond and are usually actor ligands, although some alkyl ligands behave as spectators. Our aim will be to understand the general dependence of the behavior of alkyl ligands on the metal center and the ligand’s substituents. Using this knowledge, we can make meaningful comparisons between related metal alkyl complexes and educated predictions about their likely behavior.
    • Metal Hydrides
      Metal-hydrogen bonds are ubiquitous X-type ligands in organometallic chemistry. There is much more than meets the eye to most M-H bonds: although they’re simple to draw, they vary enormously in polarization and pKa. They may be acidic or hydridic or both, depending on the nature of the metal center and the reaction conditions. In this post, we’ll develop some heuristics for predicting the behavior of M-H bonds and discuss their major modes of reactivity.
    • N-heterocyclic Carbenes
      N-heterocyclic carbenes (NHCs) exhibit their unique structure, properties, and steric tunability. Unlike most metal carbenes, NHCs are typically unreactive when coordinated to a metal (with some exceptions). Like phosphines, they are commonly used to modulate the steric and electronic properties of metal complexes. In fact, the similarities between NHCs and phosphines are notable. Overall, few ligands are as effective as NHCs at ramping up the electron density on a metal center while remaining i
    • Odd-numbered π Systems
      Odd-numbered π systems—most notably, the allyl and cyclopentadienyl ligands—are formally LnX-type ligands bound covalently through one atom (the “odd man out”) and datively through the others. This formal description is incomplete, however, as resonance structures reveal that multiple atoms within three- and five-atom π systems can be considered as covalently bound to the metal.
    • Phosphines
      Phosphines ligands are most notable for their remarkable electronic and steric tunability and their “innocence”—they tend to avoid participating directly in organometallic reactions, but have the ability to profoundly modulate the electronic properties of the metal center to which they’re bound
    • π Systems
      In contrast to the spectator L-type ligands we’ve seen so far, π systems most often play an important role in the reactivity of the OM complexes of which they are a part (since they act in reactions, they’re called “actors”). π Systems do useful chemistry, not just with the metal center, but also with other ligands and external reagents.
    • σ Complexes
      Ligands can, shockingly enough, bind through their σ electrons in an L-type fashion. This binding mode depends as much on the metal center as it does on the ligand itself.