Element-carbenes

The first group 13 (IIIA) element-carbene complex to be reported was an imi-dazol-2-ylidene-alane complex (Scheme 8.23). Based on NMR data, it was suggested that the imidazole fragment has an electronic structure that is intermediate between those of the free carbene and imidazolium ion. The use of an imidazol-2-... 

It is often difficult to deduce from the restricted experimental data the main trends in reactivity. Theoretical calculations could give the needed information to fill these gaps. In other words, they could be used to sometimes interpolate scarce experimental data, e.g. in studying substituent effects. To examine general trends in the series of Group 14 elements carbene analogs, data for silylenes and even for carbenes are presented in this section for some cases. 

M. F. Lappert, R S. Rowe, The Role of Group 14 Elements Carbene Analogues in Transition Metal Chemistry", Coord Chem. Rev. 1990,100,267. 

The reactivities of the substrate and the nucleophilic reagent change vyhen fluorine atoms are introduced into their structures This perturbation becomes more impor tant when the number of atoms of this element increases A striking example is the reactivity of alkyl halides S l and mechanisms operate when few fluorine atoms are incorporated in the aliphatic chain, but perfluoroalkyl halides are usually resistant to these classical processes However, formal substitution at carbon can arise from other mecharasms For example nucleophilic attack at chlorine, bromine, or iodine (halogenophilic reaction, occurring either by a direct electron-pair transfer or by two successive one-electron transfers) gives carbanions These intermediates can then decompose to carbenes or olefins, which react further (see equations 15 and 47) Single-electron transfer (SET) from the nucleophile to the halide can produce intermediate radicals that react by an SrnI process (see equation 57) When these chain mechanisms can occur, they allow reactions that were previously unknown Perfluoroalkylation, which used to be very rare, can now be accomplished by new methods (see for example equations 48-56, 65-70, 79, 107-108, 110, 113-135, 138-141, and 145-146)... 

Due to the inherent unsymmetric arene substitution pattern the benzannulation reaction creates a plane of chirality in the resulting tricarbonyl chromium complex, and - under achiral conditions - produces a racemic mixture of arene Cr(CO)3 complexes. Since the resolution of planar chiral arene chromium complexes can be rather tedious, diastereoselective benzannulation approaches towards optically pure planar chiral products appear highly attractive. This strategy requires the incorporation of chiral information into the starting materials which may be based on one of three options a stereogenic element can be introduced in the alkyne side chain, in the carbene carbon side chain or - most general and most attractive - in the heteroatom carbene side chain (Scheme 20). 

The second option involves the incorporation of either chiral amines or chiral alcohols into the heteroatom-carbene side chain (R ), which represents the most versatile approach to diastereoselective benzannulation. The optically pure (2R,3R)-butane-2,3-diol was used to tether the biscarbene complex 37. The double intramolecular benzannulation reaction with diphenylbutadiyne allowed introduction of an additional stereogenic element in terms of an axis... 

The tetrasulfides R R MS4 with M=Si, Ge, Sn, or Pb bearing bulky substituents on the group 14 element were synthesized by the reaction of the corresponding divalent species R R M, which are heavier analogues of the carbenes, with elemental sulfur (see Scheme 1) [11-20]. The divalent species... 

Diazoalkanes are u.seful is precursors to ruthenium and osmium alkylidene porphyrin complexes, and have also been investigated in iron porphyrin chemistry. In an attempt to prepare iron porphyrin carbene complexes containing an oxygen atom on the /(-carbon atom of the carbene, the reaction of the diazoketone PhC(0)C(Ni)CH3 with Fe(TpCIPP) was undertaken. A low spin, diamagnetic carbene complex formulated as Fe(TpCIPP)(=C(CH3)C(0)Ph) was identified by U V-visible and fI NMR spectroscopy and elemental analysis. Addition of CF3CO2H to this rapidly produced the protonated N-alkyl porphyrin, and Bit oxidation in the presence of sodium dithionitc gave the iron(II) N-alkyl porphyrin, both reactions evidence for Fe-to-N migration processes. ... 

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... 

On the other hand, the calculation for the relative stabilities of H2Si=S shows that the silanethione form (H2Si=S, 0.0 kcal mol-1) is more stable than both s-cis-HSiSH (12.0 kcal moP1) and s-trans-HSiSH (9.3 kcal moP1) isomers.12 Thus, the relative stability of heavy ketones to their carbene type isomers is considerably influenced by the combination of the Group 14 and Group 16 elements. 

Finally, the possibility of building the M=C bond into an unsaturated metallacycle where there is the possibility for electron delocalization has been realized for the first time with the characterization of osmabenzene derivatives. For these reasons then, it seemed worthwhile to review the carbene and carbyne chemistry of these Group 8 elements, and for completeness we have included discussion of other heteroatom-substituted carbene complexes as well. We begin by general consideration of the bonding in molecules with multiple metal-carbon bonds. 

Carbenes form stable complexes with many metals in the periodic table of the elements, and gold is no exception. In fact, the chemistry of this class of organogold compounds for some time has been one of the fastest growing subdisciplines. While the corresponding chapters were still short in previous accounts,1 2 the inventory for this review is now particularly rich and diverse.230 As for other classes of carbene complexes, this upsurge is based on expectations for potential applications in various fields such as NLO materials, liquid crystalline phases, and catalysis. Where applicable, this is indicated for each of the entries in this chapter. 

One Au-C bond in bis(thiazol-2-ylidene)gold cations is cleaved in the reaction with elemental iodine to give the corresponding (carbene)AuI complex and a 2-iodo-thiazolium salt, while chlorine and bromine oxidize the gold center to the gold(m) state.267... 

In considering catalyzed olefin-cyclopropane interconversions, an important question arises concerning thermodynamic control and the tendency (or lack thereof) to attain a state of equilibrium for the system. Mango (74) has recently estimated the expected relative amounts of ethylene and cyclopropane for various reaction conditions and concluded that the reported results were contrary to thermodynamic expectation. In particular, the vigorous formation of ethylene from cyclopropane (16) at -78°C was stated to be especially unfavored. On the basis of various reported observations and considerations, Mango concluded that a reaction scheme such as that in Eq. (26) above (assuming no influence of catalyst) was not appropriate, because the proper relative amounts of cyclopropanes and olefins just do not occur. However, it can be argued that the role of the catalyst is in fact an important element in the equilibration scheme, for the proposed metal-carbene and [M ] species in Eq. (26) are neither equivalent nor freely interconverted under normal reaction conditions. Consequently, all the reaction pathways are not simultaneously accessible with ease, as seen in the published literature, and the expected equilibria do not really have an opportunity for attainment. In such a case, absence of thermodynamic control should not a priori deny the validity of Eq. (26). 

The ring system 24 especially exemplifies a nucleophilic carbene, since, as Breslow showed already more than 40 years ago,47 it is the structural element that is responsible for the activity of vitamin Bi48... 

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