The Organometallic Reader

Dedicated to the teaching and learning of modern organometallic chemistry.

Posts Tagged ‘oxidative addition

Oxidative Addition of Polar Reagents

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Organometallic chemistry has vastly expanded the practicing organic chemist’s notion of what makes a good nucleophile or electrophile. Pre-cross-coupling, for example, using unactivated aryl halides as electrophiles was largely a pipe dream (or possible only under certain specific circumstances). Enter the oxidative addition of polarized bonds: all of a sudden, compounds like bromobenzene started looking a lot more attractive as starting materials. Cross-coupling reactions involving sp2– and sp-hybridized C–X bonds beautifully complement the “classical” substitution reactions at sp3 electrophilic carbons. Oxidative addition of the C–X bond is the step that kicks off the magic of these methods. In this post, we’ll explore the mechanisms and favorability trends of oxidative additions of polar reagents. The landscape of mechanistic possibilities for polarized bonds is much more rich than in the non-polar case—concerted, ionic, and radical mechanisms have all been observed.

Concerted Mechanisms

Oxidative additions of aryl and alkenyl Csp2–X bonds, where X is a halogen or sulfonate, proceed through concerted mechanisms analogous to oxidative additions of dihydrogen. Reactions of N–H and O–H bonds in amines, alcohols, and water also appear to be concerted. A π complex involving η2-coordination is an intermediate in the mechanism of insertion into aryl halides at least, and probably vinyl halides too. As two open coordination sites are necessary for concerted oxidative addition, loss of a ligand from a saturated metal complex commonly precedes the actual oxidative addition event.

Concerted oxidative addition of aryl halides and sulfonates.

Concerted oxidative addition of aryl halides and sulfonates.

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Oxidative Addition: General Ideas

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A critical difference between the transition metals and the organic elements is the ability of the former to exist in multiple oxidation states. In fact, the redox flexibility of the transition metals and the redox obstinacy of the organic elements work wonderfully together. Why? Imagine the transition metal as a kind of matchmaker for the organic elements. Transition metals can take on additional covalent bonds (oxidation), switch out ligands (substitution), then release new covalent bonds (reduction). The resulting organic products remain unfazed by the metal’s redox insanity. Talk about a match made in heaven!

The following series of posts will deal with the first step of this process, oxidation. More specifically, we’ll discuss the oxidation of transition metals via formal insertion into covalent bonds, also known as oxidative addition (OA). Although we often think of oxidative addition as an elementary reaction of organometallic chemistry, it is not an elementary mechanistic step. In fact, oxidative addition can proceed through a variety of mechanisms. Furthermore, any old change in oxidation state does not an oxidative addition make (that almost rhymes…). Formally, the attachment of an electrophile to a metal center (e.g., protonation) represents oxidation, but we shouldn’t call this oxidative addition, since two ligands aren’t entering the fray. Instead, we call this oxidative ligation (OL).

Oxidative addition involves formal bond insertion and the introduction of two new ligands to the metal. Oxidative ligation, OTOH, involves the coordination of only one new ligand, an electrophile.

Oxidative addition involves formal bond insertion and the introduction of two new ligands to the metal. Oxidative ligation, OTOH, involves the coordination of only one new ligand, an electrophile.

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Epic Ligand Survey: σ Complexes

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Epic Ligand Survey: Sigma ComplexesIn this post, we’ll investigate ligands that, 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—to see why, we need only recognize that σ complexes look like intermediates in concerted oxidative additions. With a slight reorganization of electrons and geometry, an L-type σ ligand can become two X-type ligands. Why, then, are σ complexes stable? How can we control the ratio of σ complex to X2 complex in a given situation? How does complexation of a σ bond change the ligand’s properties? We’ll address these questions and more in this post.

General Properties

The first thing to realize about σ complexes is that they are highly sensitive to steric bulk. Any old σ bond won’t do; hydrogen at one end of the binding bond or the other (or both) is necessary. The best studied σ complexes involve dihydrogen (H2), so let’s start there.

Mildly backbonding metals may bind dihydrogen “side on.” Like side-on binding in π complexes, there are two important orbital interactions at play here: σH–Hdσ and dπ→σ*H–H. Dihydrogen complexes can “tautomerize” to (H)2 isomers through oxidative addition of the H–H bond to the metal.

Orbital interactions and L-X2 equilibrium in σ complexes.

Orbital interactions and L-X2 equilibrium in σ complexes.

H2 binding in an L-type fashion massively acidifies the ligand—changes in pKa of over thirty units are known! Analogous acidifications of X–H bonds, which we touched on in a previous post, rarely exhibit ΔpKa > 5. What gives? What’s causing the different behavior of X–H and H–H ligands? The key is to consider the conjugate base of the ligand—in particular, how much it’s stabilized by a metal center relative to the corresponding free anion. The principle here is analogous to the famous dictum of organic chemistry: consider charged species when making acid/base comparisons. Stabilization of the unhindered anion H by a metal is much greater than stabilization of larger, more electronegative anions like HO– and NH2– by a metal. As a result, it’s more favorable to remove a proton from metal-complexed H2 than from larger, more electronegative X–H ligands. Read the rest of this entry »

Written by Michael Evans

April 10, 2012 at 10:58 am

Epic Ligand Survey: Odd-numbered π Systems

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Epic Ligand Survey: Odd-numbered Pi SystemsOdd-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. To illustrate the plurality of equally important resonance structures for this class of ligands, we often just draw a curved line from one end of the π system to the other. Yet, even this form isn’t perfect, as it obscures the possibility that the datively bound atoms may dissociate from the metal center, forming σ-allyl or ring-slipped ligands. What do the odd-numbered π systems really look like, and how do they really behave? We’ll try to get to the bottom of these questions in the remainder of this post.

General Properties

Allyls are often actor ligands, most famously in allylic substitution reactions. The allyl ligand is an interesting beast because it may bind to metals in two ways. When its double bond does not become involved in binding to the metal, allyl is a simple X-type ligand bound covalently through one carbon—basically, a monodentate alkyl! Alternatively, allyl can act as a bidentate LX-type ligand, bound to the metal through all three conjugated atoms. The LX or “trihapto” form can be represented using one of two resonance forms, or (more common) the “toilet-bowl” form seen in the general figure above. I don’t like the toilet-bowl form despite its ubiquity, as it tends to obscure the important dynamic possibilities of the allyl ligand.

Can we use FMO theory to explain the wonky geometry of the allyl ligand?

Can we use FMO theory to explain the wonky geometry of the allyl ligand?

The lower half of the figure above illustrates the slightly weird character of the geometry of allyl ligands. In a previous post on even-numbered π systems, we investigated the orientation of the ligand with respect to the metal and came to some logical conclusions by invoking FMO theory and backbonding. A similar treatment of the allyl ligand leads us to similar conclusions: the plane of the allyl ligand should be parallel to the xy-plane of the metal center and normal to the z-axis. In reality, the allyl plane is slightly canted to optimize orbital overlap—but we can see at the right of the figure above that π2dxy orbital overlap is key. Also note the rotation of the anti hydrogens (anti to the central C–H, that is) toward the metal center to improve orbital overlap. Read the rest of this entry »

Epic Ligand Survey: Metal Hydrides

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Epic Ligand Survey: Metal HydridesMetal-hydrogen bonds, also known (misleadingly) as metal hydrides, 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 (acidity, radical reactions, migratory insertion, etc.). We’ll also touch on the most widely used synthetic methods to form metal hydrides.

General Properties

Metal hydrides run the gamut from nucleophilic/basic to electrophilic/acidic. Then again, the same can be said of X–H bonds in organic chemistry, which may vary from mildly nucleophilic (consider Hantzsch esters and NADH) to extremely electrophilic (consider triflic acid). As hydrogen is what it is in both cases, it’s clear that the nature of the X fragment—more specifically, the stability of the charged fragments X+ and X—dictate the character of the X–H bond. Compare the four equilibria outlined below—the stabilities of the ions dictate the position of each equilibrium. By now we shouldn’t find it surprising that the highly π-acidic W(CO)5 fragment is good at stabilizing negative charge; for a similar reason, the ZrCp2Cl fragment can stabilize positive charge.*

Metal-hydrogen bonds may be either hydridic (nucleophilic) or acidic (electrophilic). The nature of other ligands and the reaction conditions are keys to making predictions.

Metal-hydrogen bonds may be either hydridic (nucleophilic) or acidic (electrophilic). The nature of other ligands and the reaction conditions are keys to making predictions.

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