Carbenes in coordination chemistry

The chemistry of carbenes in coordination chemistry can be approached from various perspectives. Their use as ligands is still expanding and from a perspective of organic reaction mechanism may not always be of high impact. Therefore, we will focus here on the nature of the earbene and its influence on the chemical transformations as well as on organic transformations that involve carbenes and take place in the coordination sphere of a metal or on a metalloid. 

The usefulness of carbene in coordination chemistry is well established and a comprehensive survey of all the complexes bearing a carbene as ligand is clearly out of the scope of this book in general and of this chapter in particular. Thus, we will focus here on some chosen studies in which the use of carbene ligands has a particular impact on the reaction mechanism. 

The chiral center most frequently encountered is the asymmetric carbon atom, a tetrahedral C atom, bonded to four different substituents. Chiral centers of this type are known for many other elements (4). However, chiral centers are also found in other polyhedra, e.g., the metal atoms in octahedral compounds containing three bidendate chelate ligands. Chirality axes, present in the atrop isomers of ortho-substituted biaryls, occur in coordination chemistry in appropriately substituted aryl, pyridyl, and carbene metal complexes. Well known examples of planar chirality in organometallic chemistry are ferrocenes, cymantrenes, and benchrotrenes containing two different substituents in 1,2- or 1,3-positions relative to each other (5-5). 

A widely used precursor for Rh(I) and Ir(I) in coordination chemistry is the [MC1(C0D)]2 dimer (120). In the presence of either free NHC or in situ generated carbene from the alcohol adduct or the combination imidazolium salt and base, the dimer was cleaved giving rise to [(NHC)MCl(COD)] (121) (Scheme 20). The presence of labile COD allowed for further modification of the metal coordination sphere. For example, under CO atmosphere the COD ligand was rapidly removed, leaving two CO binding the metal center. The... 

Rh(OEP)H reacts with CNR (R = Me, n-Bu,) to give the adduct Rh(OEP)-(H)CNR (which has no parallel in CO chemistry) which then slowly transforms to the formimidoyl insertion product, Rh(OEP)C(H)=NR. The dimer Rh(OEP))2 reacts with CNAr (Ar = 2.6-Cf,H3Mc2) in aqueous benzene to give the carbamoyl product. Rh(OEP)C(0)NHAr (characterized by an X-ray crystal structure) together with the hydride, which it.self reacts further with the isocyanide. This is suggc.sted to form via a cationic carbene intermediate, formed by attack of HiO on coordinated CNAr in concert with disproportionation to Rh(III) and Rh(l). 

Low-coordinate species of the main group elements of the second row such as carbenes, olefins, carbonyl compounds (ketones, aldehydes, esters, amides, etc.), aromatic compounds, and azo compounds play very important roles in organic chemistry. Although extensive studies have been devoted to these species not only from the physical organic point of view but also from the standpoints of synthetic chemistry and materials science, the heavier element homologues of these low-coordinate species have been postulated in many reactions only as reactive intermediates, and their chemistry has been undeveloped most probably due to... 

The development of the chemistry of carbene complexes of the Group 8a metals, Ru, Os, and Ir, parallels chemistry realized initially with transition metals from Groups 6 and 7. The pioneering studies of E. O. Fischer and co-workers have led to the characterization of many hundreds of carbene complexes in which the heteroatoms N, O, and S are bonded to the carbene carbon atoms. The first carbene ligands coordinated to Ru, Os, and Ir centers also contained substituents based on these heteroatoms, and in this section the preparation and properties of N-, O-, S-, and Se-substituted carbene complexes of these metals are detailed. 

Carbene ligands, especially the A-heterocyclic carbenes, are regarded as universal ligands in coordination and organometallic chemistry. They are able to bind to a wide variety of metal centers in various oxidation states, as well as to both stabilize and activate metal centers of key intermediates in the catalytic cycles of various organic... 

Reports on the coordination chemistry of A-heterocyclic carbene-containing metal complexes started to appear as long ago as 1968,50,51 while metal-free carbenes have only been isolated very recently.52 In view of the fact that the general chemistry and applications of organic carbenes and related metal complexes in chemical synthesis have been reviewed several times recently,53-57 examples limited only to those carbene complexes with silver(i) have been discussed. Nevertheless, it is worth mentioning that the developments in silver(i) A-heterocyclic carbenes have also been reviewed recently by Lin.5... 

In view of the versatility of A-heterocyclic carbenes as ligands and their structural diversity in silver(i) coordination chemistry, an extension of the work to ligands with two or more carbene moieties was reported. A dinuclear silver(i) complex 52 (Figure 21) with an o-phenylenedimethylene-bridged bis(carbene) ligand has been synthesized in 66% yield from silver(i) oxide and the bis(imidazolium) salt.88 The reaction to synthesize 52 has to be carried out in... 

Carbenes are electron-deficient two-coordinate carbon compounds that have two nonbonding electrons at one carbon. In the ground state, the two unshared electrons may be either in the same orbital and have antiparallel spins (singlet state S), or in two different orbitals with parallel spins (triplet state T). They can be considered as typical representatives of reactive intermediates and have found a broad range of applications in synthetic chemistry. 

Abstract A-Heterocyclic carbenes (NHCs) have developed into an important class of ligands in transition metal coordination chemistry. They have been employed successfully as spectator ligands in various catalytically active metal complexes and as organocatalysts. In this chapter we present some important synthetic methods for the preparation of various NHCs and their metal complexes. 

Among the polydentate carbene ligands, particular interest has recently been placed on cyclic polycarbenes. ImidazoUum precursors like 23 [89] or 24 [90, 91], which upon C2 deprotonation would lead to tetradentate or even hexadentate double-pincer NHC ligands, have been prepared. Their interesting coordination chemistry will be discussed in Sect. 4. Finally, Arnold et al. developed and reviewed NHC ligands which are functionalized with additional anionic (alkoxide or amido) donor groups [92]. 

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