Ruthenium and Osmium Arenes

Octahedral ruthenium(III) complexes are relatively inert towards ligand substitution. The reduction from ruthenium(III) to ruthenium(II) as an activation process prior to DNA binding was first suggested in the late 1970s by Clarke and coworkers [35, 46-50]. 

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 

Chart 2 General structure of Ru11 and Os11 piano-stool arene complexes 

In general, Ru11 and Os11 arene complexes show promising cytotoxic activity against human ovarian cancer cell lines, some of them as potent as cisplatin and carboplatin. Some structure-activity relationships have been established 

The rate and extent of hydrolysis of the Ru-Z bond are highly dependent on the nature of Z, more labile leaving groups giving rise to faster hydrolysis [53]. 

---

E3.5 Molecular and crystal structures of ruthenium and osmium arene clusters... 

The crystal structure of (ij4-cyclooctatetraene)(hexamethylbenzene)ruthenium (16) indicates bonding as a tetrahapto ligand60. For this complex and similar iron-, ruthenium- and osmium-(ij4-cyclooctatetraene)(arene) complexes, their XH and 13C NMR spectra exhibit only a single signal for the cyclooctatetraene ligand at temperatures as low as —145 °C. Using this temperature, the barrier-to-metal migration is estimated to be <6.6 kcal mol 1. 

Once the ruthenium or osmium arene organometallic complex is activated with the formation of the aqua species, [Ru/Os(r 6-arene)(OH2)(X)(Y)] (Chart 3), the metal becomes a potential centre for nucleophilic attack by biomolecules. The binding of Run/Osn arene complexes to nucleobases is of special interest, since DNA could be the ultimate target for this class of organometallic complexes. A number of studies have confirmed this postulate [86, 87] and investigated in detail such interactions [53, 54, 72, 88-93]. DNA interactions of Ru and Os arene complexes have recently been reviewed [94],... 

Organometallic Chemistry of Arene Ruthenium and Osmium Complexes... 

Arene ruthenium and osmium complexes play an increasingly important role in organometallic chemistry. They appear to be good starting materials for access to reactive arene metal hydrides or 16-electron metal(O) intermediates that have been used recently for carbon-hydrogen bond activation. Various methods of access to cyclopentadienyl, borane, and carborane arene ruthenium and osmium complexes have been reported. 

T/6-Arene ruthenium and osmium offer specific properties for the reactivity of arene ligand. The activation toward nucleophiles or electrophiles is controlled mainly by the oxidation state of the metal (II or 0). Recently, from classic organometallic arene ruthenium and osmium chemistry has grown an area making significant contributions to the chemistry of cyclo-phanes. These compounds are potential precursors of organometallic polymers which show interesting electrical properties and conductivity. 

The possibility of coordination of a two-electron ligand, in addition to arene, to the ruthenium or osmium atom provides a route to mixed metal or cluster compounds. Cocondensation of arene with ruthenium or osmium vapors has recently allowed access to new types of arene metal complexes and clusters. In addition, arene ruthenium and osmium appear to be useful and specific catalyst precursors, apart from classic hydrogenation, for carbon-hydrogen bond activation and activation of alkynes such compounds may become valuable reagents for organic syntheses. 

---