Complexes of Ruthenium and Osmium Containing η2–η6 Hydrocarbon Ligands: (i) Complexes not Containing Cyclobutadiene, Cyclopentadienyl or η-Arene Coligands

Bennett, Martin A.

doi:10.1016/b978-008046519-7.00062-9

Cited by 2 publications

(1 citation statement)

References 219 publications

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“…The syntheses of both sandwich and half-sandwich complexes were made available through the experimental works of Bennett and colleagues (Bennett 1966, 1995a,b, 1997, Bennett et al 1980, 1981, 1985, 1991a,b, 1992, 1995, 1996a,b, 1997, 1998a,b, 2000, 2001, 2005, Pertici et al 1998, Hirano et al 2002, 2009, 2012, Shin et al 2003, Widegren et al 2003, Adams and Bennett 2006. Ru-arene complexes, especially those with cyclopentadienyl, ruthenocene, and benzenoid η 6 -electron donor ligands, were all experimentally feasible using Bennett's synthesis .…”

Section: Heterocyclic Nitrogen Donor Ligandsmentioning

confidence: 99%

Development of ruthenium-based complexes as anticancer agents: toward a rational design of alternative receptor targets

Adeniyi

Ajibade

2016

Reviews in Inorganic Chemistry

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AbstractIn the search for novel anticancer agents, the development of metal-based complexes that could serve as alternatives to cisplatin and its derivatives has received considerable attention in recent years. This becomes necessary because, at present, cisplatin and its derivatives are the only coordination complexes being used as anticancer agents in spite of inherent serious side effects and their limitation against metastasized platinum-resistant cancer cells. Although many metal ions have been considered as possible alternatives to cisplatin, the most promising are ruthenium (Ru) complexes and two Ru compounds, KP1019 and NAMI-A, which are currently in phase II clinical trials. The major obstacle against the rational design of these compounds is the fact that their mode of action in relation to their therapeutic activities and selectivity is not fully understood. There is an urgent need to develop novel metal-based anticancer agents, especially Ru-based compounds, with known mechanism of actions, probable targets, and pharmacodynamic activity. In this paper, we review the current efforts in developing metal-based anticancer agents based on promising Ru complexes and the development of compounds targeting receptors and then examine the future prospects.

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Section: Heterocyclic Nitrogen Donor Ligandsmentioning

confidence: 99%

Development of ruthenium-based complexes as anticancer agents: toward a rational design of alternative receptor targets

Adeniyi

Ajibade

2016

Reviews in Inorganic Chemistry

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Alkene Complexes of Divalent and Trivalent Ruthenium Stabilized by Chelation. Dependence of Coordinated Alkene Orientation on Metal Oxidation State

et al. 1998

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Zinc amalgam reduction of tris(acetylacetonato)ruthenium(III), [Ru(acac)3], in the presence of the chelating olefinic N- and O-donor ligands (LL‘) 2-vinyl-N,N-dimethylaniline, o-CH2CHC6H4NMe2 (1), 2-isopropenyl-N,N-dimethylaniline, o-CH2C(CH3)C6H4NMe2 (2), 3-butenyldimethylamine, CH2CHCH2CH2NMe2 (3), 2-allylpyridine, CH2CHCH2C5H4N (4), isomesityl oxide (4-methyl-4-penten-2-one), CH2C(CH3)CH2COCH3 (5), 2-methoxystyrene, o-CH2CHC6H4OMe (6), and 3-butenylmethyl ether, CH2CHCH2CH2OCH3 (7) gives the corresponding bis(acetylacetonato)ruthenium(II) complexes [Ru(acac)2(LL‘)] (8−14). These undergo one-electron oxidation by cyclic voltammetry to the corresponding cations [Ru(acac)2(LL‘)]+, the process being reversible at both room temperature and −60 °C. The cations were isolated as deep blue, paramagnetic PF6 or SbF6 salts from the oxidation of the ruthenium(II) precursors 8−12 and 14 with Ag+ or [FeCp2]+ salts; they are the first stable alkene complexes of ruthenium(III). At both oxidation levels, coordination of the prochiral alkene gives rise to a pair of diastereomers, labeled a, b at the Ru(II) level, a + , b + at the Ru(III) level, whose redox potentials E 1/2 (Ru3+/2+) differ by ca. 100 mV. The equilibrium a/b ratio at the Ru(II) level is ca. 1:9, although for 8, 10, and 11 this is established only after several hours at ca. 100 °C, the ratio in the complexes immediately after isolation being ca. 2:3. Selective removal of the more easily oxidized diastereomer of the 2-vinyl-N,N-dimethylaniline complex 8a by treatment of a 2:3 mixture with ca. 0.5 equiv of Ag+ provides pure 8b, which undergoes reversible one-electron oxidation at −60 °C to 8b + . Above −10 °C, 8b + isomerizes to an equilibrium mixture (ca. 85:15) of 8a + and 8b + , as shown by UV−visible spectroelectrochemistry. Thus, both diastereomeric preference and rate of interconversion are strongly dependent on the oxidation state (number of metal d-electrons). The metrical parameters pertaining to alkene coordination in the diastereomers 8a and 8b do not differ significantly, the metal−carbon distances being 2.159(4), 2.144(4) Å (8a), 2.142(2), 2.153(3) Å (8b) and the CC distances being 1.383(5) Å (8a) and 1.382(4) Å (8b). The corresponding distances in the Ru(III) complex [8a]+[SbF6]- [Ru−C = 2.239(6), 2.236(7) Å; CC = 1.355(9) Å] indicate that the alkene is more weakly bound than in either of its diastereomeric Ru(II) precursors.

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Complexes of Ruthenium and Osmium Containing η2–η6 Hydrocarbon Ligands: (i) Complexes not Containing Cyclobutadiene, Cyclopentadienyl or η-Arene Coligands

Cited by 2 publications

References 219 publications

Development of ruthenium-based complexes as anticancer agents: toward a rational design of alternative receptor targets

Development of ruthenium-based complexes as anticancer agents: toward a rational design of alternative receptor targets

Alkene Complexes of Divalent and Trivalent Ruthenium Stabilized by Chelation. Dependence of Coordinated Alkene Orientation on Metal Oxidation State

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