1.5- Cyclooctadiene ruthenium complex

CgHio, 1,3,5-Cyclooctatriene ruthenium complex, 22 178 CsH 2, 1,5-Cyclooctadiene ruthenium complex, 22 178 CgH]4, Cyclooctene ... 

C2H,N, Pyridine, 3,5-dimethyl-palladium complex, 26 210 CbHsNO, Benzoyl isocyanide chromium com-C HbO, Ethanone, 1-phenyl-manganese complex, 26 156-158 CBH, 02, Methyl benzoate chromium complex, 26 32 C H i, o-Xylylene magnesium complex, 26 147 ChH P, Phosphine, dimethylphenyl-iron complex, 26 61 ruthenium complex, 26 273 ChH12, 1,5-Cyclooctadiene iridium complex, 26 122 ruthenium complexes, 26 69-72, 253-256 ChH OjPS, 2-Butenedioic acid, 2-(dimethylphosphinothioyl)-dimethyl ester, manganese complex, 26 163... 

For example, the tail-to-tail dimerization of methyl acrylate was catalyzed by ruthenium complexes such as RuHCl(C0)(Pz-Pr3)2/CF3S03Ag or even RuC13 and gave dimethyl hexenedioate isomers. Efficient catalytic systems such as Ru(rf-naphthalene)(COD)/CH3CN, where COD is cyclooctadiene, selectively led to the diester 2 in 75% yield [1] (Eq. 1). 

The 1,5 cyclooctadiene complex [Cp Ru(jj rf--C Yiu) (CO)]OTf was isolated upon treatment of Cp Ru(j)" -butadiene)X (X = Cl, Br) with butadiene, AgOTf, and CO. A similar [4-1-4] cycloaddition (a thermally forbidden reaction see Woodward-Hoffmann Rules)) is observed when Cp Ru(isoprene)Cl is treated with iso-prene, AgOTf, and CO. Likewise, the reaction of 1,3-pentadiene with Cp Ru( ) -l,3-pentadiene)Cl results in linear dimerization to form [Cp Ru(4-methyl-(l,3-jj 6-8-j) )-nonadienediyl)]OTf. These types of dimerization occur with both stoichiometric and catalytic amounts of the ruthenium complex. ... 

Described here is the preparation of (l,5-cyclooctadiene)tricarbonylrutheni-um and its use in the synthesis of tricarbonyl(/7-diene)ruthenium complexes. 

The complex functions as the most suitable source of the tricarbonylruthe-nium unit in syntheses of tricarbonyl(7-diene)ruthenium complexes. Derivatives of 1,3-cyclohexadiene, 1,3-cycloheptadiene, cycloheptatriene, cyclooc-tatetraene, 2,4,6-cycloheptatrien-l-one, bicyclo[3.2. l]octa-2,6-diene, bicyclo-[3.2. l]octa-2,4-diene, and butadiene have been prepared by displacement of 1,5-cyclooctadiene. 

Although in most instances CO2 is an inert solvent, it is also the ideal mediiun in which to carry out reactions of CO2 itself. 3-Hexyne in SC CO2 has been shown to react in the presence of Ni(COD)2PPh2(CH2)4PPh2 (COD = cyclooctadiene) to afford the cyclic ester shown (Scheme 1) with the nickel complex acting as a template [51]. The hydrogenation of CO2 catalysed by a ruthenium complex and NEta can be advantageously carried out in SC CO2, where the high concentration of H2 makes enhanced activity possible [52]. 

Ruthenium-catalyzed hydroacylation of 1,3-dienes with aromatic and heteroaromatic aldehydes occurs in relatively good yields to afford the corresponding fi, /-unsaturated ketones . Isoprene and benzaldehyde were treated with 4 mol% Ru(COD)(COT) (COD = 1,5-cyclooctadiene, COT = 1,3,5-cyclooctatriene) and 4 mol% PPhs under argon for 40 hours to give 54% 80 (equation 41). The key intermediate is an acyl- ) -(allyl)ruthenium complex which undergoes reductive elimination to give the corresponding... 

C4H,o, 1,3,5-Cyclooctatriene, ruthenium complex, 22 178 CgHl2, 1,5-Cyclooctadiene, iridium complexes, 23 127 rhodium complex, 23 127, 129 ruthenium complex, 22 178 C8H]4, Cyclooctene, iridium complex, 21 102 CsH16, Cyclooctane, boron complex, 22 199... 

Acetylenic compounds form adducts with acrylic acid derivatives, catalysed by a ruthenium complex with 1,5-cyclooctadiene (cod) and 1,3,5-cyclooctatriene (cot), as shown in reaction 10. ... 

Oxidative addition of allyl and vinyl ethers to zero-valent ruthenium complex also takes place under mild conditions. The reaction of Ru(cod)(cot) [cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene] with allyl phenyl ether or phenyl ortho-tolyl ether in the presence of PMea results in cleavage of the C-0 bond to give a (r -allyl)(aryloxo)ruthenium(II) complex, Ru(OAr)(r/ -C3H5)(PMe3)3 (Scheme 3.40) [77]. When allyl 2,6-xylyl ether is employed in this reaction, further C-H bond activation takes place to give an oxaruthenacycle... 

In the reaction of the a-amino acid derivative 73 with 1,5-cyclooctadiene catalyzed by ruthenium complex 2 depicted in Scheme 2.29, an enyne CM followed by an RCM was coupled in a domino manner with an initial ROM of the cyclic diene [17b,cj. The resulting enantiomericaUy pure 1,3-cyclohexadiene 74 was then used to construct the diketopiperazine core of the scabrosin epidithiodiketopiperazine antibiotics [17cj. 

The kinetics of the ADMET reaction is not amenable to study by many traditional means, as these polymerizations are mostly conducted in bulk. The most effective way to measure the kinetics of the polymerization is to monitor the volume of evolved ethylene. This technique has been used to probe the difference in activity between [Mo] 2 and [Ru]l for ADMET polymerization of 1,9-decadiene [37]. At 26 °C in bulk monomer, [Mo] 2 promotes ADMET polymerization of 1,9-decadiene at a rate approximately 24 times that of [Ru]l. Additionally, [Mo] 2 polymerizes 1,5-hexadiene 1.7 times faster than 1,9-decadiene, while [Ru]l only cyclodimerizes 1,5-hexadiene to 1,5-cyclooctadiene. Monomers with coordinating functionality, specifically ethers and sulfides, were also investigated. Predictably, these monomers did not undergo polymerization as rapidly as hydrocarbon monomers however, this difference was dramatically more pronounced with [Ru]l than with [Mo]2. In fact, the dialkenyl sulfide monomers that were studied completely shut down the polymerization with [Ru]l, whereas the catalytic activity of [Mo]2 was only slightly lowered. This reduction in polymerization rate is most likely due to coordination of the heteroatom to the vacant coordination site of [Ru] 1, following phosphine dissociation. This reversible coordination of heteroatoms to the ruthenium complex likely occurs both intramolecularly and intermolecularly. Conversely, the steric bulk of the ligands in [Mo] 2 makes it less likely to intramolecularly form a coordinate complex, despite molybdenum being far more electrophilic than ruthenium. 

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