Metal-carbene complexes Classification

During the past few decades, a wide variety of molecules with transition metal-carhon mulhple bonds have been studied. The chemistry of doubly bonded species - carbenes - is particularly interesting because it leads to several synthetically important transformations, and for this reason, metal carbenes are the main subject of this chapter. Our discussion begins with a classification of metal-carbene complexes based on electronic structure, which provides a way to understand their reactivity patterns. Next, we summarize the mechanistic highlights of three metal-carbene-mediated reactions carbonyl olefinafion, olefin cyclopropanafion, and olefin metathesis. Throughout the second half of the chapter, we focus mainly on ruthenium-carbene olefin metathesis catalysts, in part because of widespread interest in the applications of these catalysts, and in part because of our expertise in this area. We conclude with some perspectives on the chemistry of metal carbenes and on future developments in catalysis. 

It is well known that metal carbenes can be classified as Fisher and Schrock carbenes. The classification is mainly based on the n electron density distribution on the M = C moiety (Scheme 4.2). On the basis of the n electron density distribution, carbene complexes of the Fisher-type (E) are normally electrophilic at the carbene carbon while carbene complexes of the Schrock-type (F) are nucleophilic at the carbene carbon. Similarly, metal vinylidenes could also be classified into the two types Fisher-type (G) and Schrock-type (H). The majority of isolated metal vinylidenes belong to the Fisher-type. On the basis of the 7t electron density distribution shown in... 

For a long time metal carbenes have been either classified as Fischer- or Schrock carbenes, depending on the oxidation state of the metal. Since the introduction of N-heterocycHc carbene complexes this classification needs to be extended because of the very different electronic character of these ligands. Carbenes—molecules with a neutral dicoordinate carbon atom—play an important role in all fields of chemistry today. The first examples in the field of organic chemistry were published by Doering and Hoffmann in the 1950s [1], while Fischer and Maasbol introduced them to organometallic chemists about ten years later [2,3]. But it took another 25 years until the first carbenes could be isolated [4-8]. 

Classification of carbene complexes as Fischer or Schrock perhaps focuses too much on their differences and too little on their similarities. Both contain a metal-carbon bond of order greater than one. Whether the carbene carbon tends to seek or provide electrons will depend on the extent of it bonding involving the metal and the carbon substituents. Some carbene complexes lie between the Fischer/Schrock extremes, behaving in some reactions as nucleophiles and in others as electrophiles.69... 

There are several parallels between the chemistries of the carbene and carbyne ligands. The classification of carbyne complexes into two major structural types—Fischer and Schrock—is perhaps the most obvious of these parallels. Complex 64 represents the prototypical Fischer carbyne complex Ccarbyne bonded to a low-valent metal with Ji-accepting CO ligands attached. Structure 65, on the other hand, is a classic example of a Schrock carbyne complex because a high-valent metal is present with electron-donating ligands attached. Atoms attached to Ccaibyne helpful in distinguishing between Fischer and Schrock carbene complexes (i.e., heteroatoms for the former and H and C for the latter), are less important in the case of carbyne complexes. It is convenient to classify carbyne complexes... 

The nucleophilic-electrophilic/Schrock-Fischer distinctions have been extremely useful throughout the development of metal-carbene chemistry because they provide a way to categorize metal carbenes and rationalize their reactivity patterns [6]. Yet, as an increasing variety of complexes are studied, it is becoming clear that these classifications represent only the prototypical complexes that were inihally discovered. We now know of many examples with intermediate characteristics and reactivity profiles, such as electrophilic species that lack heteroatom stahilizahon and even complexes like (Cp)(CO)2Re=CHR that display ambiphilic reachvity, meaning that this rhenium carbene reacts with both nucleophiles and electrophiles (Eq. 4.1) [7]. 

While major advances in the area of C-H functionalization have been made with catalysts based on rare and expensive transition metals such as rhodium, palladium, ruthenium, and iridium [7], increasing interest in the sustainability aspect of catalysis has stimulated researchers toward the development of alternative catalysts based on naturally abundant first-row transition metals including cobalt [8]. As such, a growing number of cobalt-catalyzed C-H functionalization reactions, including those for heterocycle synthesis, have been reported over the last several years to date (early 2015) [9]. The purpose of this chapter is to provide an overview of such recent advancements with classification according to the nature of the catalytically active cobalt species involved in the C-H activation event. Besides inner-sphere C-H activation reactions catalyzed by low-valent and high-valent cobalt complexes, nitrene and carbene C-H insertion reactions promoted by cobalt(II)-porphyrin metalloradical catalysts are also discussed. 

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