Ruthenium complex directly bonded

Unfunctionalized alkenes have posed more of a problem, as they have no polar moiety which can coordinate to the catalyst. Such an additional metal binding site next to the C = C bond has proven to be crucial for directing coordination to the catalyst and, therefore, rhodium and ruthenium complexes, which are highly selective for functionalized alkenes, generally provide only low enan-tioselectivity for this class of substrates. 

The same ethylidene ruthenium complex, as well as its iron congener, is alternatively obtained through direct protonation of the dimetallacycles 64a (M = Fe) and 64b (M = Ru) (64). In this case, the carbonyl alkyne carbon-carbon bond is broken irreversibly to give the cationic /x, 17s-vinyl complexes 65a and 65b, which undergo nucleophilic attack by hydride (NaBFLi) to produce complexes of methylcarbene (63a,b) (Scheme 21a). Deuterium-labeling experiments prove that the final compounds arise from initial hydride addition to the /3-vinylic carbon of 65. However, isolation of small amounts of the 7j2-ethylene complex 66 indicates that hydride attack can also occur at the a-vinylic carbon (64). 

The formation of metal vinylidene complexes directly from terminal alkynes is an elegant way to perform anti-Markovnikov addition of nucleophiles to triple bonds [1, 2], The electrophilic a-carbon of ruthenium vinylidene complexes reacts with nucleophiles to form ruthenium alkenyl species, which liberate this organic fragment on protonolysis (Scheme 1). 

Protonation of 322 with tetrafluoroboric acid in diethyl ether gives the cyclohexadienyl derivative 325 in 70% yield. Treatment of 325 with lithium aluminum hydride yields the biscyclohexadienyl osmium(II) complex 326. Treatment of 322 with PMe3 at 60°C gives the hydridophenyl osmium-(II) complex 181, rather than the expected arene bistrimethylphosphine osmium(O) compound, via intramolecular C—H bond activation of the benzene ligand (192,193) (Scheme 38). Compound 181 as well as the analogous ruthenium complex (92) have also been obtained directly by cocondensation of osmium or ruthenium atoms with benzene and tri-methylphosphine (62) [Eq. (44)]. 

Experiments with cyclooctatetraene and its methyl and phenyl derivatives have demonstrated that reaction with certain ruthenium carbonyl complexes can occur with transannular bonding to give pentalene complexes directly.253,264 The structures of these unique molecules have been confirmed by X-ray crystallography. 

Besides Cu and Rh, various other metals are known to catalyze the decomposition of diazo compounds [6,7,8,9,10]. Palladium complexes, e.g., are efficient catalysts for the cyclopropanation of electron-deficient C-C double bonds with diazoalkanes [19,20, 21], in contrast to Cu and Rh catalysts which are better suited for reactions with electron-rich olefins. Unfortunately, attempts to develop chiral Pd catalysts for enantioselective cyclopropanation have not been successful so far [22]. More promising results have been obtained with cobalt and ruthenium complexes. These and other chiral metal catalysts, that have been studied besides Cu and Rh complexes, are discussed in chap. 16.3. The same chapter also covers a new direction of research that has recently been taken with the development of catalytic enantioselective Simmons-Smith reactions. 

The remarkable stability of ruthenium complexes could, further, be exploited for direct arylations between simple arenes as pronucleophiles and inexpensive, broadly available phenols as proelectrophiles. Notably, this operationally simple dehydrative direct arylation was achieved with a highly chemo- and regioselective ruthenium catalyst, along with a sulfonyl chloride, and proceeded overall through the functionalizations of both C-H as well as C-OH bonds (Scheme 29) [85],... 

Ueno S, Mizushima E, Chatani N, Kakiuchi F (2006) Direct observation of the oxidative addition of the aryl carbon-oxygen bond to a ruthenium complex and consideration of the relative reactivity between aryl carbon-oxygen and aryl carbon-hydrogen bonds. J Am Chem Soc 128 16515-16517... 

A different type of metallation, directed by an acyl group at either the pyridine 3- or 4-position, uses a catalytic ruthenium complex and results in a reductive Heck-type substitution, as illustrated below. The mechanism involves insertion of the metal into a C-H bond. The process is non-polar and works equally well with electron-rich heterocycles, for example indole. ... 

Direct evidence for the oxidative addition of allyl carboxylates to a zero-valent ruthenium complex with the allyl-0 bond cleavage, has been obtained by the reaction of Ru(cod)(cot) (cot = 1,3,5-cyclooctatriene) with allyl carboxylates in the presence of tertiary phosphine under ambient conditions to give Ru(OCOR)()7 -C3H5)L3 [55], where Ru( 7 -C8Hio)L3 acts as an intermediate for the reaction (Scheme 3.29) [56]. 

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