Organometallic ruthenium -arene

The organometallic ruthenium-arene fragments improved the aqueous solubility of the otherwise insoluble porphyrins without modifying the photophysical properties of the photosensitizer. Additionally, the presence of the ruthenium on the porphyrins facilitated uptake into melanoma cells [160]. 

Ang WH, Daldini E, Scolaro C, Scopelliti R, Juillerat-Jeannerat L, Dyson PJ (2006) Development of organometallic ruthenium-arene anticancer drugs that resist hydrolysis. Inorg Chem 45 9006-9013... 

Dougan SJ, Sadler PJ (2007) The design of organometallic ruthenium arene anticancer agents. Chimia 61 704-715... 

Liu H-K, Bemers-Price SJ, Wang F, Parkinson JA, Xu J, Bella J, Sadler PJ (2006) Diversity in guanine-selective DNA binding modes for an organometallic ruthenium arene complex. Angew Chem Int Ed Engl 45 8153-8156... 

Ang WH, Daldini E, Juillerat-Jeanneret L, Dyson PJ (2007) Strategy to tether organometallic ruthenium-arene anticancer compounds to recombinant human serum albumin. Inorg Chem 46(22) 9048-9050... 

Consequently, organometallic ruthenium(II) and osmium(II) arene complexes have recently attracted interest as anticancer agents [51]. The presence of a 7i-bonded arene in Ru11 (and Os11) complexes can have a dramatic influence on their chemical reactivity. There is a delicate balance between electron donation from the arene into the empty Ru 4d orbitals and back-donation from the filled 4d6 orbitals into vacant arene orbitals. This is influenced by the donor-acceptor power of the arene (e.g. hexamethylbenzene as a strong donor, in contrast to biphenyl which may act as acceptor) and by the other ligands on Ru11 which can influence the... 

Novel picolinate derivatives have been synthesised that show hydrolysis rates intermediate between the slow values for the complexes with /V,/V-chelating ligands, and the rapidly-hydrolysing complexes with 0,0- or N,0- amino acidlike chelating ligands. For these organometallic osmium complexes, the hydrolysis rates fall into the range of the active ruthenium-arene relatives (Fig.l) [66]. 

Therrien et al. have developed organometallic ruthenium porphyrin compounds for anticancer photodynamic therapy. These combine synergistically the photodynamic action of porphyrins with the DNA damage-related cytotoxicity of Run-arene... 

Yan YK, Melchart M, Habtemariam A, Sadler PJ (2005) Organometallic chemistry, biology and medicine ruthenium arene anticancer complexes. Chem Commun 4764-4776... 

Mendoza-Ferri M-G, Hartinger CG, Eichinger RE, Stolyarova N, Severin K, Jakupec MA, Nazarov AA, Keppler BK (2008) Influence of the spacer length on the in vitro anticancer activity of dinuclear ruthenium-arene compounds. Organometallics 27 2405-2407... 

Hu W, Luo Q, Ma X, Wu K, Liu J, Chen Y, Xiong S, Wang J, Sadler PJ, Wang F (2009) Arene control over thiolate to sulfinate oxidation in albumin by organometallic ruthenium anticancer complexes. Chem Eur J 15 6586-6594... 

Little is known about the chemical nature of the recently isolated carbon clusters (C o> C70, Cg4, and so forth). One potential application of these materials is as highly dispersed supports for metal catalysts, and therefore the question of how metal atoms bind to C40 is of interest. Reaction of C o with organometallic ruthenium and platinum re nts has shown that metals can be attached directly to the carbon framework. Ihe native geometry of transition metal, and an x-ray difi action analysis of the platinum complex [(CgHg)3P]2Pt( () -C6o) C4HgO revealed a structure similar to that known for [(C4Hs)3P]2Pt( n -ethylene). The reactivity of C40 is not like that of relatively electron-rich planar aromatic molecules su( as benzene. The carbon-carbon double bonds of C40 react like those of very electron-deficient arenes and alkcnes. 

Ruthenium arenes are another interesting class of organometallics with proven anticancer activity. The most active complex [( 7 -biphenyl)Ru(ethylene-diamine)Cl] 1 (Scheme 11) had an activity comparable to Garboplatin against a human ovarian cancer cell line. " The interaction of this compound with different biomolecules has been studied, and again, DNA has been suggested as the primary target. It is, however, unclear at present... 

Two main families of organometallic ruthenium(II)-arene complexes (see Fig. 43.1) were developed and studied by Sadler [3, 4] (RM complexes) and Dyson [5, 6] (RAPTA complexes), in which the basic structures present the piano-stool geometry and their reactivity toward biological targets is based on the leaving chloride ligands, as happens with cisplatin. Nevertheless, these two families of compounds besides the similarity of their structure present different characteristics. 

Ku9ukbay, H., Cebnkaya, B., Guesmi, S., Dixneuf, P.H., New (carbene)ruthenium-arene complexes preparation and uses in catalytic synthesis of furans, Organometallics 1996, 15 2434-2439. 

Nazarov, A. A. et al. Anthracene-Tethered Ruthenium(II) Arene Complexes as Tools To Visualize the Cellular Localization of Putative Organometallic Anticancer Compounds. Inorg. Chem. 51, 3633-3639 (2012). 

---