Complexation of 1,4,5,8,9,10-hexahydroanthracene (HHA) to iron or ruthenium: a bis(diene)diiron HHA geometry, hydroaromatic ruthenium compounds related to Ru(.eta.6-THA)Cl2(DMSO) (THA = 1,4,9,10-tetrahydroanthracene; DMSO = dimethyl sulfoxide), and Ru3(CO)12-catalyzed HHA rearrangements

Beasley, Timothy J.; Brost, Ron D.; Chu, Chit Kay; Grundy, Stephen L.; Stobart, Stephen R.

doi:10.1021/om00035a052

Cited by 12 publications

(6 citation statements)

References 2 publications

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“…The IR spectrum of complex 4 showed a band at 1101 cm −1 assignable to the S−O stretching frequency for S-bonded sulphoxide . This is at higher frequency compared to the free ligand (ν S−O = 1050 cm −1 ), thus confirming unequivocally that the DMSO is bound through the S. , S-coordination of DMSO has been reported to predominate in Ru II (η 6 -arene) species. − …”

Section: Resultsmentioning

confidence: 71%

“…38 This is at higher frequency compared to the free ligand (ν S-O = 1050 cm -1 ), thus confirming unequivocally that the DMSO is bound through the S. 39,40 S-coordination of DMSO has been reported to predominate in Ru II (η 6arene) species. [41][42][43][44] Complex 5, [Ru(η 6 -C 6 H 5 (C 6 H 4 )NH 2 )(en)(OH)] þ , was formed during a basic titration, by adding strong base (0.1 M NaOH) to an aqueous solution of complex 2 (vide infra). It was characterized by 1 H NMR in aqueous solution at pH > 9 (see Supporting Information, Figure S2).…”

Section: Resultsmentioning

confidence: 99%

“…1 H NMR (DMSO-d 6 ): δ 7.38 (d, 1H, J = 7.5 Hz), δ 7.16 (t, 1H, J = 7.5 Hz), δ 6.79 (d, 1H, J = 7.5 Hz), δ 6.67 (t, 1H, J = 7.5 Hz), δ 6.22 (d, 2H, J = 6 Hz), δ 6.13 (t, 1H, J = 6 Hz), δ 5.95 (t, 2H, J = 6 Hz), δ 5. 42 [Ru(η 6 :η 1 -C 6 H 5 (C 6 H 4 )NH 2 )(en)]Cl 2 (2). Complex 1, [Ru(η 6 : η 1 -C 6 H 5 (C 6 H 4 )NH 2 )Cl 2 ], (119 mg, 0.35 mmol) was suspended in 95% aqueous methanol (2 mL).…”

Section: Methodsmentioning

confidence: 99%

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Controlling the Reactivity of Ruthenium(II) Arene Complexes by Tether Ring-Opening

Pizarro¹,

Melchart²,

Habtemariam³

et al. 2010

Inorg. Chem.

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The closed- and open-tethered Ru(II) eta(6)-arene complexes [Ru(II)(eta(6):eta(1)-C(6)H(5)(C(6)H(4))NH(2))(en)]Cl(2) (2) and [Ru(II)(eta(6)-C(6)H(5)(C(6)H(4))NH(2))Cl(en)]Cl (3), where en is ethylenediamine, have been synthesized and their X-ray structures determined. Interconversion between 2 and 3, that is, tethered-arene ring-closure and ring-opening, in different solvents has been investigated. Complex 2 opens in dimethylsulfoxide (DMSO) by solvent-induced dissociation of the NH(2) group of the pendant arm. In methanol, however, equilibrium between 2 and 3 is reached after 12 h when both species coexist in solution in a ratio of 2:1 (open/closed). In water (pH 7), complete ring closure of 3 to 2 at 298 K occurs in less than 2 h. The tether ring of complex 2 opens at basic pH and closes at neutral pH. Complex 2 opens over time (18 h) in concentrated HCl. The opening-closing process is fully reversible in the pH range 2-12. Density Functional Theory calculations have been used to obtain insights into the electronic structure of complexes 2 and 3, their UV-vis properties, and their stability compared to their aqua derivatives. Control of tether-ring-opening can contribute toward a strategy for activation and for achieving cytotoxic selectivity of ruthenium arene anticancer drugs.

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Section: Resultsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Controlling the Reactivity of Ruthenium(II) Arene Complexes by Tether Ring-Opening

Pizarro¹,

Melchart²,

Habtemariam³

et al. 2010

Inorg. Chem.

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“…[( η 6 -C 14 H 14 )RuCl 2 ] 2 . 1,4,5,8,9,10-Hexahydroanthracene (1.0 g, 5.43 mmol) was added to a solution of RuCl 3 ·3H 2 O (0.84 g, 3.18 mmol) in dry ethanol (60 mL) and refluxed under Ar for 48 h. Filtration of the hot reaction mixture gave a yellow-brown solid which was washed with fresh ethanol (2 mL) followed by diethyl ether (4 × 10 mL) and dried under vacuum. Yield: 0.96 g (85.5%).…”

Section: Methodsmentioning

confidence: 99%

Organometallic Ruthenium(II) Diamine Anticancer Complexes: Arene-Nucleobase Stacking and Stereospecific Hydrogen-Bonding in Guanine Adducts

et al. 2002

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Organometallic ruthenium(II) arene anticancer complexes of the type [(eta(6)-arene)Ru(II)(en)Cl][PF(6)] (en = ethylenediamine) specifically target guanine bases of DNA oligomers and form monofunctional adducts (Morris, R., et al. J. Med. Chem. 2001). We have determined the structures of monofunctional adducts of the "piano-stool" complexes [(eta(6)-Bip)Ru(II)(en)Cl][PF(6)] (1, Bip = biphenyl), [(eta(6)-THA)Ru(II)(en)Cl][PF(6)] (2, THA = 5,8,9,10-tetrahydroanthracene), and [(eta(6)-DHA)Ru(II)(en)Cl][PF(6)] (3, DHA = 9,10-dihydroanthracene) with guanine derivatives, in the solid state by X-ray crystallography, and in solution using 2D [(1)H,(1)H] NOESY and [(1)H,(15)N] HSQC NMR methods. Strong pi-pi arene-nucleobase stacking is present in the crystal structures of [(eta(6)-C(14)H(14))Ru(en)(9EtG-N7)][PF(6)](2).(MeOH) (6) and [(eta(6)-C(14)H(12))Ru(en)(9EtG-N7)][PF(6)](2).2(MeOH) (7) (9EtG = 9-ethylguanine). The anthracene outer ring (C) stacks over the purine base at distances of 3.45 A for 6 and 3.31 A for 7, with dihedral angles of 3.3 degrees and 3.1 degrees, respectively. In the crystal structure of [(eta(6)-biphenyl)Ru(en)(9EtG-N7)][PF(6)](2).(MeOH) (4), there is intermolecular stacking between the pendant phenyl ring and the purine six-membered ring at a distance of 4.0 A (dihedral angle 4.5 degrees). This stacking stabilizes a cyclic tetramer structure in the unit cell. The guanosine (Guo) adduct [(eta(6)-biphenyl)Ru(en)(Guo-N7)][PF(6)](2).3.75(H(2)O) (5) exhibits intramolecular stacking of the pendant phenyl ring with the purine five-membered ring (3.8 A, 23.8 degrees) and intermolecular stacking of the purine six-membered ring with an adjacent pendant phenyl ring (4.2 A, 23.0 degrees). These occur alternately giving a columnar-type structure. A syn orientation of arene and purine is present in the crystal structures 5, 6, and 7, while the orientation is anti for 4. However, in solution, a syn orientation predominates for all the biphenyl adducts 4, 5, and the guanosine 5'-monophosphate (5'-GMP) adduct 8 [(eta(6)-biphenyl)Ru(II)(en)(5'-GMP-N7)], as revealed by NMR NOE studies. The predominance of the syn orientation both in the solid state and in solution can be attributed to hydrophobic interactions between the arene and purine rings. There are significant reorientations and conformational changes of the arene ligands in [(eta(6)-arene)Ru(II)(en)(G-N7)] complexes in the solid state, with respect to those of the parent chloro-complexes [(eta(6)-arene)Ru(II)(en)Cl](+). The arene ligands have flexibility through rotation around the arene-Ru pi-bonds, propeller twisting for Bip, and hinge-bending for THA and DHA. Thus propeller twisting of Bip decreases by ca. 10 degrees so as to maximize intra- or intermolecular stacking with the purine ring, and stacking of THA and DHA with the purine is optimized when their tricyclic ring systems are bent by ca. 30 degrees, which involves increased bending of THA and a flattening of DHA. This flexibility makes simultaneous arene-base stacking and N7-covalent binding compati...

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“…The starting materials [(η 6 -arene)RuX 2 ] 2 [X = Cl or I and arene = p -cymene ( p -cym), hexamethylbenzene (hmb), and biphenyl (bip)] were prepared according to literature methods. , o -Phenylenediamine ( o -pda) and 4,5-dimethyl- o -phenylenediamine (dmpda) were purchased from Sigma-Aldrich and glutathione (GSH) from Acros Organics. Ethanol and methanol were dried over Mg/I 2 .…”

Section: Methodsmentioning

confidence: 99%

Ruthenium(II) Arene Anticancer Complexes with Redox-Active Diamine Ligands

et al. 2009

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The synthesis and characterization of ruthenium(II) arene complexes of the general formula [(eta(6)-arene)Ru(XY)Z](+), where arene = p-cymene (p-cym), hexamethylbenzene (hmb), or biphenyl (bip), XY = o-phenylenediamine (o-pda), o-benzoquinonediimine (o-bqdi), or 4,5-dimethyl-o-phenylenediamine (dmpda), and Z = Cl, Br, or I, are reported (complexes 1-6). In addition, the X-ray crystal structures of [(eta(6)-p-cym)Ru(o-pda)Cl]PF(6) (1) and [(eta(6)-hmb)Ru(o-bqdi)Cl]PF(6) (3PF(6)) are described. The Ru-N distances in 3PF(6) are significantly shorter [2.033(4) and 2.025(4) A] compared to those in 1 [2.141(2) and 2.156(2) A]. All of the imine complexes (3-5) exhibit a characteristic broad (1)H NMR NH resonance at ca. delta 14-15. Complex 1 undergoes concomitant ligand-based oxidation and hydrolysis (38% after 24 h) in water. The oxidation also occurs in methanol. The iodido complex [(eta(6)-p-cym)Ru(o-bqdi)I]I (4) did not undergo hydrolysis, whereas the chlorido complex 3 showed relatively fast hydrolysis (t(1/2) = 7.5 min). Density functional theory calculations showed that the total bonding energy of 9-EtG in [(eta(6)-p-cym)Ru(o-pda)(9-EtG-N7)](2+) (1EtG) is 23.8 kJ/mol lower than that in [(eta(6)-p-cym)Ru(o-bqdi)(9-EtG-N7)](2+) (3EtG). The greater bonding energy is related to the contribution from strong hydrogen bonding between the NH proton of the chelating ligand and O6 of 9-EtG (1.69 A). A loss of cytotoxic activity was observed upon oxidation of the amine ligand to an imine (e.g., IC(50) = 11 microM for 1 and IC(50) > 100 microM for 3, against A2780 ovarian cancer cells). The relationship between the cytotoxic activity and the solution and solid state structures of the imine and amine complexes is discussed.

show abstract

Complexation of 1,4,5,8,9,10-hexahydroanthracene (HHA) to iron or ruthenium: a bis(diene)diiron HHA geometry, hydroaromatic ruthenium compounds related to Ru(.eta.6-THA)Cl2(DMSO) (THA = 1,4,9,10-tetrahydroanthracene; DMSO = dimethyl sulfoxide), and Ru3(CO)12-catalyzed HHA rearrangements

Cited by 12 publications

References 2 publications

Controlling the Reactivity of Ruthenium(II) Arene Complexes by Tether Ring-Opening

Controlling the Reactivity of Ruthenium(II) Arene Complexes by Tether Ring-Opening

Organometallic Ruthenium(II) Diamine Anticancer Complexes: Arene-Nucleobase Stacking and Stereospecific Hydrogen-Bonding in Guanine Adducts

Ruthenium(II) Arene Anticancer Complexes with Redox-Active Diamine Ligands

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