The Organometallic Reader

Dedicated to the teaching and learning of modern organometallic chemistry.

Posts Tagged ‘concerted 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 of Non-polar Reagents

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How important are oxidative additions of non-polar reagents? Very. The addition of dihydrogen (H2) is an important step in catalytic hydrogenation reactions. Organometallic C–H activations depend on oxidative additions of C–H bonds. In a fundamental sense, oxidative additions of non-polar organic compounds are commonly used to establish critical metal-carbon bonds. Non-polar oxidative additions get the ball rolling in all kinds of catalytic organometallic reactions. In this post, we’ll examine the mechanisms and important trends associated with non-polar oxidative additions.

Oxidative Additions of H2

Electron-rich metal centers with open coordination sites (or the ability to form them) undergo oxidative additions with dihydrogen gas. The actual addition step is concerted, as we might expect from the dull H2 molecule! However, before the addition step, some interesting gymnastics are going on. The status of the σ complex that forms prior to H–H insertion is an open question—for some reactions it is a transition state, others a discrete intermediate. In either case, the two new hydride ligands end up cis to one another. Subsequent isomerization may occur to give a trans dihydride.

Oxidative addition of dihydrogen to Vaska's complex. Note the cis arrangement of the hydride ligands.

Oxidative addition of dihydrogen to Vaska’s complex. Note the cis arrangement of the hydride ligands.

There’s more to this little reaction than meets the eye. For starters, either pair of trans ligands in the starting complex (L/L or Cl/CO) may “fold back” to form the final octahedral complex. As in associative ligand substitution, the transition state for folding back is basically trigonal bipyramidal. As we saw before, π-acidic ligands love the equatorial sites of the TBP geometry, which are rich in electrons capable of π bonding. As a consequence, π-acidic ligands get folded back preferentially, and tend to end up cis to their trans partners in the starting complex.

Dihydrogen may approach along two distinct trajectories. Placing π-acidic ligands in the equatorial plane of the TBP transition state is favored.

Dihydrogen may approach along two distinct trajectories. Placing π-acidic ligands in the equatorial plane of the TBP transition state is favored.

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Written by Michael Evans

July 4, 2012 at 4:09 pm

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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