The Organometallic Reader

Dedicated to the teaching and learning of modern organometallic chemistry.

Posts Tagged ‘trans effect

The trans/cis Effects & Influences

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The trans effect is an ancient but venerable observation. First noted by Chernyaev in 1926, the trans effect and its conceptual siblings (the trans influence, cis influence, and cis effect) are easy enough to comprehend. That is, it’s simple enough to know what they are. To understand why they are, on the other hand, is much more difficult. I call ideas like this—which, by the way, pop up often in organometallic chemistry—”icebergs.” Their definitions are simple and easy to see; their explanations can be complex.

Definitions & Examples

Let’s begin with definitions: what is the trans effect? There’s some confusion on this point, so we need to be careful. The trans effect proper, which is often called the kinetic trans effect, refers to the observation that certain ligands increase the rate of ligand substitution when positioned trans to the departing ligand. The key word in that last sentence is “rate”—the trans effect proper is a kinetic effect. The trans influence refers to the impact of a ligand on the length of the bond trans to it in the ground state of a complex. The key phrase there is “ground state”—this is a thermodynamic effect, so it’s sometimes called the thermodynamic trans effect. Adding to the insanity, cis effects and cis influences have also been observed. Evidently, ligands may also influence the kinetics or thermodynamics of their cis neighbors. All of these phenomena are independent of the metal center, but do depend profoundly on the geometry of the metal (more on that shortly).

Kinetic trans and cis effects are shown in the figure below. In both cases, we see that X1 exhibits a stronger effect than X2. The geometries shown are those for which each effect is most commonly observed. The metals and oxidation states shown are prototypical.

The kinetic trans and cis effects in action. X1 is the stronger (trans/cis)-effect ligand in these examples.

The kinetic trans and cis effects in action. X1 is the stronger (trans/cis)-effect ligand in these examples.

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Epic Ligand Survey: N-heterocyclic Carbenes

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Epic Ligand Survey: N-heterocyclic CarbenesOur romp through the common dative ligands continues with the N-heterocyclic carbenes (NHCs). Although we’ll tackle carbenes in general in another post, NHCs deserve their own nod due to 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 innocent.

General Properties

Free NHCs contain carbon in the rarely encountered +2 oxidation state. In general, we can classify carbenes according to the nature of the two non-bonding electrons—if they are spin paired (one up and one down), the carbene is called a singlet; if their spins are parallel, we call the carbene a triplet. Whether a carbene is in the singlet or triplet state depends primarily on the difference in energy between its frontier orbitals—when the FMOs are close in energy, single occupation of each FMO (the triplet state) is likely. As the energy difference increases, the singlet state becomes more likely because the higher-energy FMO is less likely to be occupied.

FMO pictures for singlet and triplet carbenes.

FMO pictures for singlet and triplet carbenes.

How do we tinker with the FMO energies, you ask? The nature of the R groups is key. When R is electron-donating, the energy of the LUMO is raised through a fairly straightforward n → 2pz orbital interaction. An analogous interaction is responsible for the stability of carbocations adjacent to lone-pair-bearing heteroatoms (such as the oxocarbenium ion). Thanks to this orbital interaction, electron-donating groups stabilize the singlet state…and NHCs are no exception! The figure below depicts only one of two possible n → 2pz interactions in free N-heterocyclic carbenes. The LUMOs of free NHCs are quite high in energy, relative to other kinds of carbenes. Read the rest of this entry »


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