Carbyne complexes Catalytic metathesis

More recently, Schrock has reported the formation of coordinatively unsaturated Ta and W carbyne complexes (124). Like unsaturated carbene complexes, these carbyne compounds are now established as being active intermediates in a number of catalytic reactions. The discovery of acetylene metathesis reactions catalyzed by carbyne complexes (3), for example, has generated considerable interest in this class of compound. 

The metallacyclobutane mechanism of olefin metathesis has been discussed in Sections 1.3 and 3.1.7. For metathesis of acetylenes carbyne complexes are generally required (Figure 3.44), and both heterogeneous and homogeneous catalytic systems have been developed for this purpose. 

The reversible [2+2] cycloaddition of metal alkylidyne or Fischer-type metal carbyne complexes remains the only general methodology for the synthesis of metallacyclobutadiene complexes. Recent literature revolves principally around the heavier group 6 metals and the investigation of intermediates in catalytic alkyne metathesis (Scheme 25 Equation 45) <1996CHEC-II(lb)887> (W <2005OM4684>, Mo <2003JOM56>). 

In the early 1980s, Schrock prepared a series of tungsten- and molybdenum-based carbyne complexes, and demonstrated that they are viable catalysts for performing stoichiometric and catalytic alkyne metathesis [7]. With the defined carbyne complexes, he laid the foundation for the mechanistic understanding of alkyne metathesis, and was the first to demonstrate that vinyl-substituted carbyne complexes are stable [8] and that alkyne metathesis could be performed in the presence of C=C double bonds. 

The carbyne complexes [Mo(=CBu )(SAr)3] (SAr = TMT, TIPT) have been synthesized by adding 3 eq of Li[SAr] to [Mo(=CBu )Cl3(dme)] (dme = dimethoxyethane). The analogous W derivatives were made by a slightly modified route (32). The initial aim was to probe the acetylene metathesis catalytic properties of the complexes [M ( Bu KSArlg] (M = Mo, W SAr = TMT, TIPT). However, none of the complexes were active for metathesis, which was in contrast to the high activity of the analogous alkoxide compounds for metathesis. This was attributed to the stronger electron donation power of thiolate, which reduces the electrophilic nature of the metal center (32). 

Schrock et al. studied intensively the stoichiometric and catalytic metathesis of disubstituted alkynes with the carbyne W(VI) complex ( BuO)3WsC Bu, Figure 1. They also tested some monosubstituted alkynes and found that they form polyalkynes... 

Cl3(dme)WCtBu catalytic metatheses of differently substituted imines or carbodiimides occur. Consequently also linear or cyclic alkenes give catalytic metatheses with the Cl3(dme)WCtBu. Polycyclic alkenes, like norbornene, give ringopening metathesis polymerisation (ROMP) not only with CI3(dme)WCtBu, but also with Np3WCtBu and (tBuO)3WCtBu. All 3 carbyne complexes are active catalysts for the polymerisation of 1-alkynes. 

In 1976 Fischer had tested the ROMP reactions of cycloalkanes with carbyne tungsten(O) complexes as catalysts (6). With addition of Lewis acids as cocatalysts the Fischer type carbyne complexes were active in cycloalkane metathesis polymerisation. Fischer type carbyne complexes are also active catalysts for alkyne polymerisations, as found by Katz in 1984 (7). The catalytic reactions of Schrock type carbyne tungsten(VI) or molybdenum(VI) complexes were focussed on alkyne metatheses reactions (8). 

Encouraged by our results on stoichiometric and catalytic metathesis reactions of carbodiimides and imines with Fischer type carbene tungsten(O) complexes (9) we started 1984 with metathesis like reactions of the Schrock type carbyne tungsten (VI) complex Cl3(dme)WCtBu with heteroallenes (isocyanates, carbodiimides, isothiocyanates) and with heteroalkenes (imines and nitroso compounds). 

Following the catalytic metathesis of carbodiimides and isothiocyanates with Cl3(dme)WCtBu, we tested the metatheses of alkenes with this complex. Linear 1-alkenes and monocyclic alkenes (scheme 4) give catalytic metathesis with the Schrock type carbyne complex in CH2CI2 at 20°C (12). At 76 °C and in 1,2 dichloroethane as solvent the turnover frequence enhance (Table 1) (13). 

The discussed reactions of carbene and carbyne complexes show that they have essential significance as catalysts or unstable transient intermediate compounds in such catalytic processes as metathesis of olefins and other unsaturated compounds, Fischer-Tropsch synthesis, syntheses of cyclopropanes from diazoalkanes and olefins, and polymerization of olefins and alkynes as well as in organic synthesis. Except for alkynes [reaction (5.132) ] some compounds containing double bonds react with carbon monoxide and carbene ligands to form bonds with those groups. Examples of such compounds are enamines, ynamines, and Schiff bases. The JV-vinylpyrrolidone (enamine), methoxyphenylcarbene, and excess of CO (higher pressure) react to furnish enaminoketone. 

Alkyne metathesis was first observed in heterogeneous catalytic systems at high temperatures. " Early homogeneous catalytic systems, which consisted of a mixture of molybdenum hexacarbonyl and a phenol, required a lower, but still high, temperature (Scheme 8.129). " Alternatively, the reaction could be photochemical. It is assumed that a carbyne complex is generated as the active catalyst. 

In the preparative section 3.2 devoted to metal-carbene complexes, it is shown how the a-elimination reaction from high oxidation state early-transition-metal-alkyl complexes is one of the general methods of synthesis of Schrock s Ta and Nb alkylidene complexes. The other direction, formation of an alkylidene from an alkylidyne complex, can also be a valuable route to metal alkylidenes. For instance, Schrock s arylamino-tungsten-carbynes can be isomerized to imido-tungsten-carbene by using a catalytic amount of NEts as a base. These compounds are precursors of olefin metathesis catalysts by substitution of the two Cl ligands by bulky alkoxides (dimethoxyethane then decoordinates for steric reasons), and this route was extended to Mo complexes ... 

The preparation and study of metallacycles has been a subject of active investigation for organometallic chemists. We have just seen one example where metallacycle formation is a key step in a catalytic process and there are several others most notably, olefin metathesis. The metal acts as a geometrical and electronic template in these reactions. For unsaturated metallacycles there are interesting questions concerning delocalization [29]. Certain metal carbynes can react with acetylene to give metallacyclobutadienes as intermediates [30]. One such example of an insoluble molecule is the tungstenacyclobutadiene complex, 18.36 [31]. The compound is quite stable and not very reactive (in contrast to cyclobutadienes... 

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