Ruthenium carboxylates

Figure 1.33 A possible orbital sequence for dinuclear ruthenium carboxylates.

Figure 1.34 The structure of trinuclear oxo-centred ruthenium carboxylates. For clarity, only one of each pair of bridging carboxylates is shown.

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... 

Binuclear [RuX2(arene)]2 (1) and mononuclear RuX2(L) (arene) (3) derivatives have been shown to be useful precursors for access to alkyl-or hydrido(arene)ruthenium complexes. The latter are key compounds for the formation of arene ruthenium(O) intermediates capable of C—H bond activation leading to new hydrido and cyclometallated ruthenium arene derivatives. Arene ruthenium carboxylates appear to be useful derivatives of alkyl-ruthenium as precursors of hydrido-ruthenium complexes their access is examined first. 

Figure 48 Packing of dinculear ruthenium carboxylates in the Colh phase.

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 ... 

Miktrriya M, Yoshioka D, Honda M (2006) Magnetic interactions in one-, two-, and three-dimensiortal assemblies of dinuclear ruthenium carboxylates. Coord Chem Rev 250 2194-2211. doi 10.1016/j.ccr.2006.01.011... 

AMphatic primary and secondary alcohols were more efficiently oxidized using trinuclear ruthenium carboxylates, RujO(OiCR>6L (L = HjO, Ph3P) as the catalysts ". With lower aliphatic alcohols, e.g. 1-propanol, 2-propanol and 1-butanol, activities were ca. 10 times higher than with RuClj and RUCI2 (Ph3P)3. 

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