Complexes, alkyne-metal metathesis

Alkenylsilanes, mainly vinyl silanes and allyl silanes or related compounds, being widely used intermediates for organic synthesis can be efficiently prepared by several reactions catalyzed by transition-metal complexes, such as dehy-drogenative silylation of alkenes, hydrosilylation of alkynes, alkene metathesis, silylative coupling of alkenes with vinylsilanes, and coupling of alkynes with vinylsilanes [1-7]. Ruthenium complexes have been used for chemoselective, regioselective and stereoselective syntheses of unsaturated products. 

Perhaps the most remarkable illustration of the ability of metals to activate alkynes comes from reactions in which complete scission of the carbon-carbon triple bond occurs. On the stoichiometric level these include examples in which carbyne complexes are produced from alkyne completes as in the melt-thermolysis of CpCo(PPh3)(RCsCR) [112] or from reactions of alkynes with unsaturated metal species (Scheme 4-34) [113]. The remarkable alkyne metathesis reaction (Scheme 4-35), which involves overall cleavage and regeneration of two o-and four rt-bonds, is conceptually related. A variety of functionalized alkynes can be tolerated as metathesis substrates [114] and especially effective catalysts for these reactions are Mo(VI)-and W(VI)-carbyne complexes. Metallacyclobutadienes 64, formed by the reaction of the alkyne with a metal-carbyne complex, appear to be central intermediates in these reactions and the equilibrium between metallacycle and alkyne/metal-carbyne is observable in some cases [115]. 

Compounds 33 and 34 are readily formed from 31 by direct reaction with CpCo(CO)2. A possible reaction sequence is formation of the triene, 31, from alkyne dimerization followed by reaction with the cobalt species to give the three complexes. Reaction of 34 with alkynes yielded only cyclobutadiene complexes alkyne metathesis was not observed, probably since the carbon-to-metal bonds are too strong. 

Nitrido complexes have also been formed by metathesis and atom transfer processes. The reaction of dinitrogen with a molybdenum(III) species forms a molybdenum-nitrido complex, as shown in Equation 13.103. and described in more detail in the section of Chapter 5 on dinitrogen complexes. In a metathesis process involving related complexes, the reaction of a metal-alkylid)me complex with a nitrile extrudes an alkyne to form a metal nitride fliat adopts a dimeric structure (Equation 13.104). - Related nitrido complexes have been formed from an azabicydic compoimd that eliminates anthracene after forming the M-N bond (Equation 13.105). ... 

When coordinated to palladium, the rr-indenyl ligand tends to slip from the if - to the 77 -coordination mode, and most of the complexes synthesized show severe distortions or clear -indenyl coordination. Thus, although being a cyclopentadienyl analog, it is rare to find a true Tj -indenyl coordination to palladium, however common for other transition metals. Metathesis with Li[indenide] and ligand-substitution reactions are common preparative routes for indenyl derivatives. The insertion of an alkyne into Pd-G bonds of vinyl substituted aryls, followed by intramolecular alkene insertion, also leads to highly substituted indenyl palladium complexes. Equation (66) shows one of these examples. ... 

The currently known carbometallation chemistry of the group 6 metals is dominated by the reactions of metal-carbene and metal-carbyne complexes with alkenes and alkynes leading to the formation of four-membered metallacycles, shown in Scheme 1. Many different fates of such species have been reported, and the readers are referred to reviews discussing these reactions.253 An especially noteworthy reaction of this class is the Dotz reaction,254 which is stoichiometric in Cr in essentially all cases. Beyond the formation of the four-membered metallacycles via carbometallation, metathesis and other processes that may not involve carbometallation appear to dominate. It is, however, of interest to note that metallacyclobutadienes containing group 6 metals can undergo the second carbometallation with alkynes to produce metallabenzenes, as shown in Scheme 53.255 As the observed conversion of metallacyclobutadienes to metallabenzenes can also proceed via a Diels-Alder-like... 

The skeletal rearrangements are cycloisomerization processes which involve carbon-carbon bond cleavage. These reactions have witnessed a tremendous development in the last decade, and this chemistry has been recently reviewed.283 This section will be devoted to 7T-Lewis acid-catalyzed processes and will not deal, for instance, with genuine enyne metathesis processes involving carbene complex-catalyzed processes pioneered by Katz284 and intensely used nowadays with Ru-based catalysts.285 By the catalysis of 7r-Lewis acids, all these reactions generally start with a metal-promoted electrophilic activation of the alkyne moiety, a process well known for organoplatinum... 

Enyne metathesis is unique and interesting in synthetic organic chemistry. Since it is difficult to control intermolecular enyne metathesis, this reaction is used as intramolecular enyne metathesis. There are two types of enyne metathesis one is caused by [2+2] cycloaddition of a multiple bond and transition metal carbene complex, and the other is an oxidative cyclization reaction caused by low-valent transition metals. In these cases, the alkyli-dene part migrates from alkene to alkyne carbon. Thus, this reaction is called an alkylidene migration reaction or a skeletal reorganization reaction. Many cyclized products having a diene moiety were obtained using intramolecular enyne metathesis. Very recently, intermolecular enyne metathesis has been developed between alkyne and ethylene as novel diene synthesis. 

Although the transformation of a primary alkyne into a vinylidene complex, 2, in presence of a number of transition metal systems is well reported [2, 3], only rare examples are known for the transformation of an alkene into a carbene complex [4, 5]. Given the increased role played by vinylidene and carbene complexes as key partners in metathesis reactions and related catalytic processes [6, 7], opening up new efficient and easy synthetic routes to such complexes is an important challenge. 

There are of course borderline cases when the reacting hydrocarbon is acidic (as in the case of 1-alkynes) a direct attack of the proton at the carbanion can be envisaged. It has been proposed that acyl metal complexes of the late transition metals may also react with dihydrogen according to a o-bond metathesis mechanism. However, for the late elements an alternative exists in the form of an oxidative addition reaction. This alternative does not exist for d° complexes such as Sc(III), Ti(IV), Ta(V), W(VI) etc. and in such cases o-bond metathesis is the most plausible mechanism. 

The chemistry of alkylidene and alkylidyne complexes of early transition metals was developed by Schrock and co-workers and these complexes turned out to be of crucial importance to alkene and alkyne metathesis. Initially their research focused on tantalum complexes of the type CpTaCEIE, which after a-elimination (Figure 16.6) led to alkylidene complexes Cp(R)Cl2Ta=CHR [11]. 

Another focus of this chapter is the alkynol cycloisomerization mediated by Group 6 metal complexes. Experimental and theoretical studies showed that both exo- and endo- cycloisomerization are feasible. The cycloisomerization involves not only alkyne-to-vinylidene tautomerization but alo proton transfer steps. Therefore, the theoretical studies demonstrated that the solvent effect played a crucial role in determining the regioselectivity of cycloisomerization products. [2 + 2] cycloaddition of the metal vinylidene C=C bond in a ruthenium complex with the C=C bond of a vinyl group, together with the implication in metathesis reactions, was discussed. In addition, [2 + 2] cycloaddition of titanocene vinylidene with different unsaturated molecules was also briefly discussed. 

Metal allenylidene complexes (M=C=C=CR2) are organometallic species having a double bond betv een a metal and a carbon, such as metal carbenes (M=CR2), metal vinylidenes (M=C=CR2), and other metal cumulenylidenes like M=C=C= C=CR2 [1]. These metal-carbon double bonds are reactive enough to be employed for many organic transformations, both catalytically and stoichiometrically [1, 2]. Especially, the metathesis of alkenes via metal carbenes may be one ofthe most useful reactions in the field of recent organic synthesis [3], vhile metal vinylidenes are also revealed to be the important species in many organic syntheses such as alkyne polymerization and cycloaromatization [4, 5]. 

Mechanistic studies revealed that alkyne metathesis and ring-opening metathesis polymerization of cycloalkynes proceed via metal carbyne complexes,217 218 which is also supported by theoretical studies.219 The polymerization of PhC=CMe with NbCIs or TaCIs yields a polymer that degrades to oligomers as a result of secondary metathesis reaction. A stable polymer, however, may be synthesized with TaCIs and Ph4Sn as a cocatalyst.220... 

The chemistry of CR fragments ligating metal centers has been a topic of considerable interest since the discovery of the first alkylidyne-metal complexes in E.O. Fischer s Laboratory in 1973 (1). These ligands have been implicated in Fischer-Tropsch reactions (2) and in alkyne metathesis (5). Moreover, the isolation of stable compounds containing carbon-metal triple bonds completed the matrix of bond types represented here ... 

Alkynes can also undergo total metathesis, with cleavage of all three C=C bonds, catalysed by metal carbyne complexes at room temperature and proceeding through met-allacyclobutadiene intermediates as indicated by the framework in equation 43-6. 

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