Metallocycles

The metallocycle [67719-69-1] (24) undergoes an apparent P-elimination to a carbene-like reagent, which adds regiospecrfically to terminal acetylenes... 

When acetylthiophenes are subjected to orthomanganation, formation of the 2,3-, 103, and 3,4-, 104, metallocycles is observed [88JOM(349)197]. Complex 103 contains two coplanar live-membered heterocycles with octahedral manganese. Complex 104 is also planar. In both cases, substantial delocalization of the TT-electron density follows from the structural parameters. 

Metallocycles as intermediates in synthesis of heterocycles by transition metal-catalyzed coupling reactions under C—H bond activation 99AG(E)1698. 

Planar tetracoordination in metallocycles with group 4 and 5 metals 99ACR494. 

Titanium and zirconium chemistry has some unique features the chair conformation of the M2N4 metallocycle in the exobidentate complexes and endo-bidentate coordination. 

Metathesis is a catalyzed reaction that converts two olefin molecules into two different olefins. It is an important reaction for which many mechanistic approaches have been proposed by scientists working in the fields of homogenous catalysis and polymerization. One approach is the formation of a fluxional five-membered metallocycle. The intermediate can give back the starting material or the metathetic products via a concerted mechanism ... 

Another approach is a stepwise mechanism that involves the initial formation of a metal carbene followed by the formation of a four-membered metallocycle species ... 

From the foregoing, however, it should not be concluded that the approach of Mango and Schachtschneider is appropriate for the understanding of the metathesis reaction. The main difficulty is the supposition that the metathesis is a concerted reaction. If the reaction is not concerted, it makes no sense, of course, to correlate directly the orbitals of the reactants with those of the products. Recently, non-concertedness has been proved probable for several similar reactions, which were formerly believed to be concerted. For instance, Cassar et al. (84) demonstrated that the Rh catalyzed valence isomerization of cubane to sj/w-tricyclooctadiene proceeds stepwise. They concluded that a metallocyclic intermediate is formed via an oxidative addition mechanism ... 

The most plausible inference from these studies is to consider for the metathesis reaction a nonconcerted reaction mechanism involving a five-membered metallocyclic intermediate. In the case of the metathesis of propene, this can be visualized as follows ... 

Grubbs and Brunck (86) have recently reported experimental evidence supporting this mechanism. They have made an attempt to synthesize the proposed metallocyclic intermediate for the metathesis of ethene. Starting from the assumption that a mixture of WC1 and two equivalents of (C4H9)Li forms an active metathesis catalyst (49), they treated WC1 with 1,4-dilithio-2,3-dideuterobutane. One may expect that the following reaction would take place ... 

It is clear that a detailed mechanism for the metathesis reaction of alkenes cannot yet be given with certainty. In view of the fact that, for similar reactions which are formally cyclobutane-dialkene transformations, a nonconcerted reaction pathway has been demonstrated, a concerted fusion of two alkenes to form a cyclobutane complex and its decomposition in the same way with a change in the symmetry plane is less probable. On the basis of the information on the two other mechanisms to date, the mechanism involving a metallocyclic intermediate is more plausible than a mechanism involving carbene complexes. 

For the cyclotrimerization of alkynes, several mechanisms have been proposed. The most plausible ones are a concerted fusion of three ir-bonded alkyne molecules, and stepwise processes involving a cyclobutadiene complex or a five-membered metallocyclic intermediate (98). In the case of the cyclotrimerization of a-alkynes it is possible to discriminate between a reaction pathway via a cyclobutadiene complex and the other reaction pathways, by analysis of the products. If cyclotrimerization proceeds via a cyclobutadiene complex and if steric factors do not affect the reaction,... 

If, on the other hand, the reaction proceeds via a concerted fusion of three alkyne molecules, the 1,2,3-isomer cannot be formed. Similarly, in the case of a metallocyclic intermediate, it is to be expected that the 1,3,5- and the 1,2,4-isomers will be formed exclusively (98). 

From the above, a parallel appears to exist between the metathesis of alkenes and alkynes. Both reactions result in a redistribution of, respectively, alkylidene and alkylidyne groups. Moreover, the results obtained so far suggest that in both cases the reaction might proceed via a metallocyclic intermediate. 

Three-membered metallocycles (trinuclear clusters). S. P. Gubin, Russ. Chem. Rev. (Engl. Transl.), 1985,54,305 (169). 

When the aromatic group of the sulfoxide is replaced by a heteroaromatic group (e.g., N-methylimidazole), the internal coordination between Li—N to form a five-membered metallocycle apparently predominates over Li—O coordination to form a four-membered metallocycle . Reaction of imidazole (S)-sulfoxide 16 with benzaldehyde produces aldol 17 as the major product in which the a-H and the sulfoxide lone pair are syn (equation 14) imidazole (R)-sulfoxide 18 reacts similarly (equation 15). The stereochemical outcome of these reactions is rationalized in terms of a-lithiosulfoxides in which the reactive diastereomer (i.e., 20 and 21) is that having one diastereotopic face of the five-membered Li—N metallocycle carrying both H and sulfoxide lone pair. 

Fueled by the success of the Mn (salen) catalysts, new forays have been launched into the realm of hybrid catalyst systems. For example, the Mn-picolinamide-salicylidene complexes (i.e., 13) represent novel oxidation-resistant catalysts which exhibit higher turnover rates than the corresponding Jacobsen-type catalysts. These hybrids are particularly well-suited to the low-cost-but relatively aggressive-oxidant systems, such as bleach. In fact, the epoxidation of trans-P-methylstyrene (14) in the presence of 5 mol% of catalyst 13 and an excess of sodium hypochlorite proceeds with an ee of 53%. Understanding of the mechanistic aspects of these catalysts is complicated by their lack of C2 symmetry. For example, it is not yet clear whether the 5-membered or 6-membered metallocycle plays the decisive role in enantioselectivity however, in any event, the active form is believed to be a manganese 0x0 complex <96TL2725>. 

Dehydrohalogenation of (Ar)MCl2(Mes PH2) has also been explored in the absence of a stabilizing ligand and shown to result in the formation of 66 in the case of the Ru complex, presumable via the RU2P2 dimer 65 [104]. The formation of 68 was shown to result when the dehydrohalogenation was executed in the presence of 2-butyne, which has metallocycle 67 as likely intermediate [104]. 

The compound [Cl2SiFe(CO)4]2 is obtained from Fe(CO)j and HSiClj, in a sealed tube reaction (148). It is presumably a member of the family of Group IVB-iron metallocycles of structural type (XI) (40, 246). Two Ni... 

Certain transition metal complexes may act like carbenes, and give three-membered metallocycles with ADC compounds.74 For example, complexes 34 and 35 are readily formed. The carbene analogy also extends to the formation of 1,4-addition products (e.g., 36)7 5... 

A3-Pyrroline formation with carbonyl insertion also occurs during the reaction of /V-sulfinylarylamines with diphenylcyclopropenone in the presence of nickel carbonyl (Scheme 36).64 Phenyl isocyanate does not give a pyrroline product under these reaction conditions, hence the SO-CO exchange probably occurs within an intermediate metallocycle. The reaction... 

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