Ruthenium carboxylate complexes

Ruthenium carboxylate complexes are easily obtained under mild reaction conditions, (a) Melchart, M., Habtemariam, A., Parsons, S., Moggach, S.A. and Sadler, P.J. (2006) Inorg. Chim. Acta, 359, 3020-8 ... 

An increase of HDA concentration led to a higher rate of nanoparticle formation from Ru3(CO)i2, while an increase of PA concentration had the opposite effect. This is likely to be related to the presence of ruthenium-amine and ruthenium-carboxylate complexes as intermediates in the synthetic process. Before the formation of the nanostars, quasi-spherical and unbranched nanoparticles were first... 

Ruthenium forms four significant families of carboxylate complexes. 

The carboxylates complexes of osmium have been studied less than the ruthenium analogues [173],... 

The use of stoichiometric ruthenium-NHC complexes generated in situ from [Ruljd-COCKp-cymene)], an imidazohnm salt [4] or an imidizol(idin)ium-2-carboxylate [4] has been applied in the cyclopropanation of styrene 5 with ethyl diazoacetate (EDA) 6 (Scheme 5.2). No base was necessary when imidazolium-2 carboxylate were employed. The diastereoselectivity was low and the cis/trans ratio was around 50/50 (Table 5.1). Although the diastereoselectivity was moderate, the reaction was highly chemoselectivity as possible side reactions (homologation, dimerisation and metathesis) were totally or partially suppressed. 

It has been several decades since oxo-centered triruthenium-carboxylate complexes with triangular cluster frameworks of Ru3(p3-0)(p-00CR)6 (R = alkyl or aryl) were first isolated [1,2]. In the early 1970s, the first oxo-centered triruthenium complex was structurally characterized by Cotton through X-ray crystal structural determination [3]. Since then, oxo-centered trinuclear ruthenium-carboxylate cluster complexes with general formula [Ru30(00CR)6(L)2L ]n+ (R = aryl or alkyl, L and... 

Metatheses of 1,7-octadienes containing various functional groups are catalysed by ruthenium carbene complexes of the type 248. For instance, the alcohol 249 (R = CH2OH), the aldehyde 249 (R = CHO) and the carboxylic acid 249 (R = CO2H) are all converted into the corresponding cyclohexenes 250 in 82-88% yields (equation 127) and the heterocycles 252 (n = 0, 1 or 2) are efficiently produced from the amides 251 (equation 128)123. 

Ru-vinylidene complexes can be easily prepared by reaction of low-valent ruthenium complexes with terminal acetylenes. Treatment of the Ru(ii) complex 117 with phenylacetylene gave the Ru(iv)-vinylidene complex 118 in 88% yield (Scheme 41 ).60 The reaction of 118 with C02 in the presence of Et3N afforded selectively the Ru-carboxylate complex 120, probably via the terminal alkynide intermediate 119. 

BINAP-ruthenium dicarboxylate complexes are also efficient catalysts for asymmetric hydrogenation of enamides, a,p- and p,y-unsatu rated carboxylic acids, a-amino ketones, and a-acylaminoacrylic acids.1 2 3 4 5... 

Ruthenium complexes B are stable in the presence of alcohols, amines, or water, even at 60 °C. Olefin metathesis can be realized even in water as solvent, either using ruthenium carbene complexes with water-soluble phosphine ligands [815], or in emulsions. These complexes are also stable in air [584]. No olefination of aldehydes, ketones, or derivatives of carboxylic acids has been observed [582]. During catalysis of olefin metathesis replacement of one phosphine ligand by an olefin can occur [598,809]. 

This first section on Ru(Vl) dioxo complexes complexes concentrates on those with other 0-donor ligands periodate, tellurate and carboxylates. There is a review on ruthenium acetato complexes [552],... 

Ruthenium bipyridyl complexes are suitable photosensitizers because then-excited states have a long lifetime and the oxidized Ru(III) center has a longterm chemical stability. Therefore, Ru bipyridyl complexes have been studied intensively as photosensitizers for homogeneous photocatalytic reactions and dye-sensitization systems. The Ru bipyridyl complex, bis(2,2 -bipyridine)(2,2 -bipyri-dine-4, 4,-dicarboxylate)ruthenium(II), having carboxyl groups as anchors to the semiconductor surface was synthesized and single-crystal Ti02 photoelectrodes sensitized by this Ru complex were studied in 1979 and 1980 [5,6]. 

---