Ethylene ruthenium derivatives

Schubert98 proposed the potential use of several ruthenium containing polymers in photovoltaic devices. A ruthenium containing poly(ethylene glycol) derivative 34 was synthesized by the functionalization of 4-(3-aminopropyl)-4-methyl-2,2-bipyridine with polyethylene glycol) (M =2800, PDI=1.05), which was activated with /V,/V-carbonyldiimidazole (Scheme 19)." Applications in solid electrolytes for DSSC was proposed. Polyester 35 was incorporated with... 

RuCl2(arene)]2 complexes (1) react with 1,5-cyclooctadiene and 1,3- or 1,4-cyclohexadiene in the presence of ethanol and Na2C03 or zinc dust to give Ru°(776-arene)(V diene) compounds of type 196-198 in 60% yield [Eq. (20)] thus, this reaction appears to be the reverse of the 198-> 1 reaction [Eq. (19)]. The same reaction with ethylene leads to the bis-ethylene ruthenium(O) complex 205 (37%) (131,10). The norbornadiene complex 207 is prepared similarly from derivative 206 (125). Combination of transformations 206 - 207 [Eq. (21)] or 1 - 198 [Eq. (20)] with trans-... 

The ruthenium analogue of 47 Ru(ri5-C5Ph5)(CO)2Br (48) is also available, when Fe(CO)5 is replaced by Ru3(CO)12 [68]. A wide range of substitution products were obtained through replacement of both carbonyl and bromide ligand against two-electron ligands L such as phosphines, phosphites, and ethylene. Electrochemistry of these derivatives were studied in some detail. 

The chemistry of the 1 1 and 1 2 complexes differs with respect to hydrogenation (84,89). The 1 2 derivatives are inert to hydrogenation, while the 1 1 compounds are smoothly transformed into an ethylidene complex (see Scheme 1). This difference in behavior may well reflect the cause of differences in behavior of olefins on metal surfaces toward hydrogenation. The ethylidene complex may be converted back to the olefin adduct by reaction with trityl ion. The ethylidene adduct was first obtained for ruthenium by interaction of ethylene with H RujfCO) (89), and is structurally related to the corresponding cobalt derivatives, Co3(CO)9RC. As discussed above, the structure has been established in detail and involves a capping of the metal triangle... 

Other examples involve the immobilization of ruthenium porphyrin catalysts [74]. While Severin et al. generated insoluble polymer-embedded catalysts 16 by co-polymerizing porphyrin derivatives with ethylene glycol dimethacrylate (EGD-MA) [74 a], Che et al. linked the ruthenium-porphyrin unit to soluble polyethylene glycol (PEG) 17 [74b]. Both immobilized catalysts were employed in a variety of olefin epoxidations with 2,6-dichloropyridine N-oxide (Gl2pyNO), providing similar conversions of up to 99% and high selectivities (Scheme 4.9). 

Blechert carried out a tandem reaction of enynes in the presence of olefins instead of ethylene (Scheme 21). Treatment of cyclopentenol derivative 58a with Ic in the presence of an alkene affords 59a. The five-membered ring in estrone 58b is cleaved by Ic to give 59 and an alkene part is introduced on the six-membered C ring. However, cycloalkenyl amine derivative 60 is treated in a similar manner in the presence of an allyl alcohol derivative to give pyrrolidine derivative 61, and in this case, an alkene part is introduced on the diene moiety. Presumably, ruthenium carbene complex XVI reacts with an alkyne part to produce the pyrrolidine ring with a regioselectivity opposite to the other cases. 

Small amounts of ethylene glycol have been reported as products after ruthenium-catalyzed reactions in NMP and toluene solvents at 2000 atm (39). However, observations of minor amounts of this product must be viewed with caution unless great care is taken in the experimental procedure. For example, it was earlier reported that a catalyst derived from Ru,(CO)l2... 

Traces of ethylene glycol have been detected in catalytic solutions derived from Ru3(CO),2 in THF solvent, after reaction at pressures of 1000-1500 atm (176) a blank run containing no Ru3(CO)12 immediately preceding these experiments produced no detectable glycol. The major products of these ruthenium-catalyzed experiments were found to be methanol and methyl formate. 

The addition of certain ionic promoters to ruthenium catalytic solutions has been found to dramatically affect the rate and selectivity of CO hydrogenation. Whereas ruthenium solutions do not otherwise produce ethylene glycol as a significant product (except as its derivatives in in reactive solvents),... 

Hydroformylation - [CARBON MONOXIDE] (Vol 5) - [OXO PROCESS] (Vol 17) -of allyl alcohol [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) -catalysts for [CATALYSIS] (Vol 5) -C-19 dicarboxylic acids from [DICARBOXYLIC ACIDS] (Vol 8) -of ethylene [ETHYLENE] (Vol 9) -of ethylene [PROPYL ALCOHOLS - N-PROPYLALCOLHOL] (Vol 20) -of maleate and fumarate esters [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -phosphine catalyst [PHOSPHORUS COMPOUNDS] (Vol 18) -platinum-group metal catalysts for [PLATINUM-GROUP METALS] (Vol 19) -rhodium catalysis [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -ruthenium cmpds or catalyst [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -use of coordination compounds [COORDINATION COMPOUNDS] (Vol 7)... 

Another organometaliic derivative of 19 is formed as a minor by-product in the synthesis of 16 by treatment of Ru3(CO),2 with ethylene (48). Ru6C(CO)15(CH3CH = CH—CH = CHCH3) produced in this reaction is an octahedral cluster, with the trans.trans-2,4-hexadiene molecule coordinated to adjacent ruthenium atoms (Fig. 21). 

A sensor for organic chloride-containing compounds was constructed by immobilization of luminol or tris (2,2 bipyridyl) ruthenium (III) between a PMT and a poly (tetrafluoro) ethylene (PTFE) membrane [15], through which a stream of air was sampled by diffusion. A heated Pt filament incorporated in the gas line leading to the CL cell was used to oxidize the analytes prior to diffusion across the PTFE membrane. Detection limits for CC14, CHC13, and CH2C12 were 1.2-4 ppm. A similar device could also be used for the determination of hydrazine and its monomethyl and dimethyl derivatives or NH3 vapor. The detection limit for hydrazine was only 0.42 ppb [16]. 

This type of receptor is represented by compounds 16a,b bearing ruthenium ) bipyridine moieties. Both calixarenes [18] exhibit 1 1 binding of chloride and bromide anions (DMSO-d6), and they are especially suitable for the complexation of H2POj (X16a=2.8-104 M-1 K16b=5.2 103 M"1). On the other hand, if we compare these results with those for similar non-calixarene receptors, where the bipyridine unit is substituted by alkyl, aryl or ethylene glycol substituents, the introduction of calixarene does not bring any substantially new features into the complexation abilities of these derivatives. As shown by X-ray analysis, the anion is encapsulated within the cavity formed by amidic functions with the contributions of CH...anion interactions from the bipyridine unit. 

An interesting aspect of the bis(methyl)ruthenium complexes 33 is their tendency to allow hydride abstraction with (Ph3C)PF6. They lead to ethylene complexes 55 and 56 (46,47).The X-ray structure of 55 shows bond distances of 1.411(13) A for C=C and 1.50 A for Ru—H (46,47). The reaction probably proceeds via intermediates 53 and 54, although it was not established whether the transformation 33 - 53 involves a mono-electronic process as with WMe2(C5H5)2 (48). A similar reaction from the deuterated derivative 57 gives exclusively complex 58, configurationally... 

Norbornene derivatives bearing two alkynes undergo cascade enyne metathesis reactions when treated with a first generation ruthenium carbene and ethylene, giving heterocyclic dienes [28]. The ROM of the norbornene moiety initiates the cascade enyne RCM reactions (Scheme 14). When ethylene is replaced by a monosubstituted alkene, a single enyne RCM takes place, after the initial ROM of norbornene. 

Considerable effort has been devoted to achieving the intermolecular catalytic Pauson-Khand reaction. The mthenium complex-catalyzed reaction of an alkyne with an alkene such as ethylene or 2-norbornene under CO gave hydroquinone derivatives [79], with CO (2 mol) being introduced into the products (Eq. 11.36). This reaction is the first example of the preparation of hydroquinone derivatives by the reaction of alkynes and alkenes with CO, while hydroquinone is synthesized by the ruthenium-catalyzed reaction of 2 mol acetylene with 2 mol CO (Eq. 11.37) [80]. 

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