Metal-carbene complexes Heterocyclics

In spite of the fact that silver(i) X-heterocyclic carbene complexes were widely employed as carbene-transfer reagents for the synthesis of other transition metal carbene complexes, their synthesis could also be achieved by the reaction of silver salts with relatively more labile carbene metal complexes, albeit rare. Complexes 71a-71c were reported to be synthesized from the reaction of the corresponding pentacarbonyl(carbene)chromium(i) complexes with silver(i) hexafluorophosphate in CDC13 under inert atmosphere (Scheme 17).117... 

This article presents the principles known so far for the synthesis of metal complexes containing stable carbenes, including the preparation of the relevant carbene precursors. The use of some of these compounds in transition-metal-catalyzed reactions is discussed mainly for ruthenium-catalyzed olefin metathesis and palladium-Znickel-catalyzed coupling reactions of aryl halides, but other reactions will be touched upon as well. Chapters about the properties of metal- carbene complexes, their applications in materials science and medicinal chemistry, and their role in bioinorganic chemistry round the survey off. The focus of this review is on ZV-heterocyclic carbenes, in the following abbreviated as NHC and NHCs, respectively. 

The novel catalyst system based on palladium(O) /V-heterocyclic carbene complexes was developed by the group of Beller, in part prompted by the strong patent position of Dow on phosphine-based palladium catalysts [8]. The catalyst [37], either generated in situ from the corresponding imidazolium salt or the molecularly defined divinyldisiloxane complex [Pd(Imes)(dvds)] (Fig. 3), was used in the telomerization of 1,3-butadiene with methanol [38—40]. The /V-heterocyclic carbenes are in general better a-donor ligands and come with considerably different steric requirements than the phosphines. The [Pd(Imes)(dvds)] complex resembles the final telomer-palladium product complex and thus offers a facile and clean entry into the catalytic cycle. The metal carbene complex was shown to be... 

RCM has attracted much attention and has seen a tremendous increase in synthetic applications over the last decade <2000CR2963, 2006JOM(691)5129>. In this reaction, two C-C multiple bonds, such as double and double, or double and triple in the same molecule, are converted to unsaturated carbocycles or heterocycles in the presence of a metal carbene complex. The versatility of Schrock s molybdenum catalyst and Grubbs ruthenium complexes 68 and 69 (Scheme 10) in carbo- and heterocyclizations, respectively, of very different ring sizes were demonstrated <2000CR2963, 2006JOM(691)5129>. 

Of the three classes of divalent carbon species—free carbenes, reactive transition-metal carbene complexes (carbenoids), and stable metal carbenes—we restrict our consideration to the first two. Taking into account the fact that a fine reaction mechanism in planning the synthesis of specific molecules is of secondary importance, we discuss carbene and carbenoid reactions together. We concentrate solely on reactions and reaction sequences that result in a formation of a new heterocycle. Within subsections, the material is organized on the basis of reaction type. 

It is known from previous work that diazoalkanes can form carbene(alkylidene)-metal complexes [17, 18], cf. eq. (5). It is thus reasonable to assume that a metal-carbene 9 is formed from the (phosphine oxide-stabilized) species CH3Re 02) (eq. (5)). High oxidation-state metal carbene complexes have ample precedent, especially through the work of Schrock et al. [19], Isolation of type-8 species may be facilitated by sterically more-demanding auxiliary groups (e. g., C5H5 in place of CH3) or, by using heterocyclic carbenes of pronounced Lewis basicity (e. g., 1.3-imidazolin-2-ylidene [20]). 

Chapter 10 in the first edition covered metal carbene complexes, metathesis, and polymerization reactions. The chapter has now been split into two chapters. Chapter 10 now emphasizes the chemistry of carbene complexes new material on /V-heterocyclic carbene complexes, with applications in synthesis, has been introduced. Chapter 11 now considers metathesis and polymerization. The sections on the discovery and elucidation of n-bond metathesis have been rewritten and expanded. The discussion of both metathesis and Ziegler-Natta polymerization reactions has been considerably enhanced and brought up to date. 

Chiral catalysts with heterocyclic ligands and asymmetric synthesis of heterocycles with participation of metal carbene complexes 01JOM(617-618)98. 

As previously described, RCM is a powerful tool for the preparation of useful carbo- and heterocyclic intermediates. Almost all of the recent RCM reactions have been performed homogeneously with well-defined metal carbene complexes as catalysts. An example of the use of a heterogeneous catalyst in RCM is the synthesis of hydroazulenes such as 6 via RCM of highly functionalized diolefins (Eq. 17) catalyzed by CH3Re03/Si0i-Al703 and with heating under reflux at 80 °C [41]. 

Metal-carbyne complexes M CR are less known than metal carbenes. The carbyne can also be nucleophilic (Schrock type) or electrophilic (Fischer type). Fischer-type metal-carbynes are obtained by reaction of BF3 on a neutral Fischer-type metal-carbene complex, whereas Sehroek earbynes are often obtained by deshydrohalogenation of a Schrock-type metal-carbene eomplex. They catalyze alkyne metathesis and, in particular, give heterocycles with unsaturated substrates. 

Besides the heterocyclic monomers, mostly discussed in this chapter, this volume is also devoted to the ring-opening metathesis polymerization (ROMP). This polymerization is initiated and propagated by metal carbene complexes and metallacyclobutane complexes as shown in Scheme 2. 

Another type of metal-carbene complexes has recently attracted much attention. These have N-heterocyclic carbenes (NHC) as ligands. 

The ease of formation of the carbene depends on the nucleophilicity of the anion associated with the imidazolium. For example, when Pd(OAc)2 is heated in the presence of [BMIM][Br], the formation of a mixture of Pd imidazolylidene complexes occurs. Palladium complexes have been shown to be active and stable catalysts for Heck and other C-C coupling reactions [34]. The highest activity and stability of palladium is observed in the ionic liquid [BMIM][Brj. Carbene complexes can be formed not only by deprotonation of the imidazolium cation but also by direct oxidative addition to metal(O) (Scheme 5.3-3). These heterocyclic carbene ligands can be functionalized with polar groups in order to increase their affinity for ionic liquids. While their donor properties can be compared to those of donor phosphines, they have the advantage over phosphines of being stable toward oxidation. 

The surprising stability of N-heterocyclic carbenes was of interest to organometallic chemists who started to explore the metal complexes of these new ligands. The first examples of this class had been synthesized as early as 1968 by Wanzlick [9] and Ofele [10], only 4 years after the first Fischer-type carbene complex was synthesized [2,3] and 6 years before the first report of a Schrock-type carbene complex [11]. Once the N-heterocyclic ligands are attached to a metal they show a completely different reaction pattern compared to the electrophilic Fischer- and nucleophilic Schrock-type carbene complexes. 

During the last decade N-heterocyclic carbene complexes of transition metals have been developed for catalytic applications for many different or-... 

AT-heterocyclic carbenes show a pure donor nature. Comparing them to other monodentate ligands such as phosphines and amines on several metal-carbonyl complexes showed the significantly increased donor capacity relative to phosphines, even to trialkylphosphines, while the 7r-acceptor capability of the NHCs is in the order of those of nitriles and pyridine [29]. This was used to synthesize the metathesis catalysts discussed in the next section. Experimental evidence comes from the fact that it has been shown for several metals that an exchange of phosphines versus NHCs proceeds rapidly and without the need of an excess quantity of the NHC. X-ray structures of the NHC complexes show exceptionally long metal-carbon bonds indicating a different type of bond compared to the Schrock-type carbene double bond. As a result, the reactivity of these NHC complexes is also unique. They are relatively resistant towards an attack by nucleophiles and electrophiles at the divalent carbon atom. 

The 1,3-dipolar cycloadditions are a powerful kind of reaction for the preparation of functionalised five-membered heterocycles [42]. In the field of Fischer carbene complexes, the a,/ -unsaturated derivatives have been scarcely used in cyclo additions with 1,3-dipoles in contrast with other types of cyclo additions [43]. These complexes have low energy LUMOs, due to the electron-acceptor character of the pentacarbonyl metal fragment, and hence, they react with electron-rich dipoles with high energy HOMOs. 

Despite the fact that transition metal complexes have found wide application in the synthesis of carbo- and heterocycles, [3+3] cyclisation reactions mediated or assisted by transition metals remain almost unexplored [3, 86]. However, a few examples involving Fischer carbene complexes have been reported. In all cases, this complex is a,/J-unsaturated in order to act as a C3-synthon and it reacts with different types of substrates acting as C3-synthons as well. 

W-Heterocyclic Carbene Complexes in other Transition Metal Mediated Reactions... 

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