Controlling the molecular architecture of low nuclearity rhodium and iridium complexes using bridging NCX (X=N, O, S) ligands

Oro, Luis A.; Ciriano, Miguel A.; Pérez‐Torrente, Jesús J.; Villarroya, B. Eva

doi:10.1016/s0010-8545(99)00178-2

Cited by 34 publications

(19 citation statements)

References 123 publications

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“…Scaffolds to support and control a bimetallic arrangement may be provided by compartmental binucleating ligands that host two metal ions in suitable proximity. [1][2][3][4][5] Among the ligands that are capable of positioning two metal centers in close proximity, aromatic five-membered heterocycles containing two or three nitrogen atoms appear to be particularly suitable candidates. 1,2,4-Triazole-based ligands with chelating side arms in the 3-and 5-positions of the heterocycle are especially valuable for this purpose since the 1,2,4-triazole has a high tendency to span two metal ions, and the individual coordination spheres, as well as the metal-metal separations, can be tuned by appropriate alterations of the appended chelate substituents.…”

Section: Introductionmentioning

confidence: 99%

New palladium and platinum complexes with bioactive 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand: chemistry, antiproliferative activity and preliminary toxicity studies

2012

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The preparation and characterization of the new 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand, H(5)L(1), is described. Treatment of H(5)L(1) with K(2)PtCl(4) gave the dinuclear complex [Pt(H(3)L(1))](2), 1, but using MCl(2)(PPh(3))(2) where M = Pd or Pt, mononuclear complexes 2 and 3, of general formula [M(H(3)L(1))PPh(3)], were obtained. Subsequent reaction of the [Pd(H(3)L(1))PPh(3)] complex with PdCl(2)(PPh(3))(2) yielded a new dinuclear complex [(PPh(3))Pd(H(2)L(1))PdCl], 4. All compounds have been characterized by elemental analysis and FAB(+) spectrometry and by IR and NMR spectroscopy. The molecular structures of mononuclear complexes 2 and 3 and dinuclear complex 4 have been determined by X-ray crystallography. The new compounds synthesized have been evaluated for antiproliferative activity in vitro against NCI-H460, HepG2, MCF-7, A2780 and A2780cisR human cancer cell lines. The cytotoxicity data suggest that the H(5)L(1) ligand and [Pt(H(3)L(1))](2), complex 1, may be endowed with important cytotoxic properties since they are capable of not only circumventing cisplatin resistance in A2780cisR but also exhibit antiproliferative activity in NCI-H460. The interactions of these compounds with calf thymus DNA were investigated by UV-vis absorption and a nephrotoxic study, in LLC-PK1 cells, has also been carried out.

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Section: Introductionmentioning

confidence: 99%

New palladium and platinum complexes with bioactive 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand: chemistry, antiproliferative activity and preliminary toxicity studies

2012

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“…Very recently, reports from several groups describe the use of the Rh 2 4+ core as a building block to form both cyclic supramolecules and coordination polymers by condensation with appropriate bidentate ligands. 8 As a result of our interest in the design of effective polydentate ligands for the construction of polynuclear complexes 9 we have prepared the tetranuclear [M 4 (µ-PyS 2 ) 2 (diolefin) 4 ] (M= Rh, Ir) complexes ([M 4 ]) supported by two tridentate 2,6-pyridinedithiolate (PyS 2 2-) bridging ligands acting as six electron donors. 10 The rhodium and iridium tetranuclear complexes [M 4 ] are redox-active precursors of mixed-valence paramagnetic [M 4 ] + complexes.…”

Section: Introductionmentioning

confidence: 99%

Tetranuclear [Rh₄(μ-PyS₂)₂(diolefin)₄] Complexes as Building Blocks for New Inorganic Architectures: Synthesis of Coordination Polymers and Heteropolynuclear Complexes with Electrophilic d⁸and d¹⁰Metal Fragments

et al. 2004

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The reaction of [Rh4(mu-PyS2)2(cod)4] (PyS2 = 2,6-pyridinedithiolate, cod = 1,5-cyclooctadiene) with CF3SO3Me gave the cationic complex [Rh(4)(mu-PyS(2)Me)(2)(cod)4][CF3SO3]2 (1) with two 6-(thiomethyl)pyridine-2-thiolate bridging ligands from the attack of Me+ at the terminal sulfur atoms of the starting material. Under identical conditions [Rh4(mu-PyS2)2(tfbb)4] (tfbb = tetrafluorobenzobarrelene) reacted with CF3SO3Me to give the mixed-ligand complex [Rh(4)(mu-PyS2)(mu-PyS2Me)(tfbb)4][CF3SO3] 2. The nucleophilicity of the bridging ligands in the complexes [Rh4(mu-PyS2)2(diolefin)4] was exploited to prepare heteropolynuclear species. Reactions with [Au(PPh3)(Me2CO)][ClO4] gave the hexanuclear complexes [(PPh3)2Au2Rh4(mu-PyS2)2(diolefin)4][ClO4]2 (diolefin = cod (3), tfbb (4)). The structure of 4, solved by X-ray diffraction methods, showed the coordination of the [Au(PPh3)]+ fragments to the peripheral sulfur atoms in [Rh4(mu-PyS2)2(diolefin)4] along with their interaction with the neighbor rhodium atoms. Neutral coordination polymers of formula [ClMRh4(mu-PyS2)2(diolefin)4]n (M = Cu (5, 6), Au (7)) result from the self-assembly of alternating [Rh4(mu-PyS2)2(diolefin)4] ([Rh4]) blocks and MCl linkers. The formation of the infinite polymetallic chains was found to be chiroselective for M = Cu; one particular chain contains exclusively homochiral [Rh4] complexes. Cationic heterometallic coordination polymers of formula [MRh4(mu-PyS2)2(diolefin)4]n[BF4]n (M = Ag (8, 9), Cu (10, 11)) and [Rh5(mu-PyS2)2(diolefin)5]n[BF4]n (12, 13) result from the reactions of [Rh4] with [Cu(CH2CN)4]BF4, AgBF4, and [Rh(diolefin)(Me2CO)2]BF4, respectively. The heterometallic coordination polymers exhibit a weak electric conductivity in the solid state in the range (1.2-2.8) x 10(-7) S cm(-1).

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“…Given that H 2 Bzimt has two acidic protons, the reaction of Cp 3 Ln with 0.5 equivalents of H 2 Bzimt was also examined. The expected Bzimt 2complexes [Cp 2 Ln(THF)] 2 (m-h 2 :h 2 -Bzimt) (Ln = Yb (5), Er (6), Dy (7), Y ( 8)) were obtained in good yields (Scheme 1). Encouraged by the above results, we were interested to see if the synthesis of heteronuclear organolanthanides was accessible.…”

Section: Methodsmentioning

confidence: 99%

“…2-6 Heterocyclic thiolate ligands are very attractive in transition metal chemistry because of their flexible binding modes and interesting structural features of their complexes as well as their applications in homogeneous catalysis. [7][8][9][10][11][12] As one of the simple heterocyclic thiones, benzimidazole-2-thione (H 2 Bzimt) contains an imidazole ring together with a thiol group or two donor entities (-N C(-SH)-NH ↔ -N(H)-C( S)-N(H)). When applied as a ligand for metal complexes, they can exist as neutral or deprotonated forms (H 2 Bzimt, HBzimtand Bzimt 2-).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and controlled hydrolysis of organolanthanide complexes with mono- and dianionic benzimidazole-2-thiolate ligands

Liu

Zhang

et al. 2010

Dalton Trans.

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Treatment of Cp(3)Er with one equivalent of benzimidazole-2-thiol (H(2)Bzimt) in THF affords the monoanionic HBzimt(-) complex Cp(2)Er(η(2)-HBzimt)(THF)(2) (1). Reaction of Cp(3)Yb with two equivalents of H(2)Bzimt gives complex CpYb(η(2)-HBzimt)(2)(THF) (2) at room temperature. Treatment of Cp(3)Ln with three equivalents of H(2)Bzimt in reflux THF affords the homoleptic Ln(η(2)-HBzimt)(3)(THF)(2) (Ln = Er (3), Y (4)). Cp(3)Ln reacts with 0.5 equivalents of H(2)Bzimt to afford the dianionic Bzimt(2-) complexes [(Cp(2)Ln)(THF)](2)(μ-Bzimt) (Ln = Yb (5), Er (6), Dy (7), Y (8)) in good yields, in which the Bzimt(2-) ligand bridges the two metals in an μ-η(2):η(2) coordination mode. Interestingly, controlled hydrolysis of complexes Cp(2)Ln(η(2)-HBzimt)(THF)(2), CpLn(η(2)-HBzimt)(2)(THF) and [(Cp(2)Ln)(THF)](2)(μ-Bzimt) produces the same tetranuclear complexes [CpLn(μ(3)-OH)(μ-η(1):η(2)-HBzimt)](4) (Ln = Yb (9), Er (10), Y (11)), indicating that the hydrolysis selectivity greatly depends on the number of coordinated cyclopentadienyl groups. All complexes were characterized by elemental analysis, spectroscopic properties and X-ray single crystal diffraction analysis.

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Controlling the molecular architecture of low nuclearity rhodium and iridium complexes using bridging NCX (X=N, O, S) ligands

Cited by 34 publications

References 123 publications

New palladium and platinum complexes with bioactive 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand: chemistry, antiproliferative activity and preliminary toxicity studies

New palladium and platinum complexes with bioactive 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand: chemistry, antiproliferative activity and preliminary toxicity studies

Tetranuclear [Rh₄(μ-PyS₂)₂(diolefin)₄] Complexes as Building Blocks for New Inorganic Architectures: Synthesis of Coordination Polymers and Heteropolynuclear Complexes with Electrophilic d⁸and d¹⁰Metal Fragments

Synthesis and controlled hydrolysis of organolanthanide complexes with mono- and dianionic benzimidazole-2-thiolate ligands

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Controlling the molecular architecture of low nuclearity rhodium and iridium complexes using bridging NCX (X=N, O, S) ligands

Cited by 34 publications

References 123 publications

New palladium and platinum complexes with bioactive 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand: chemistry, antiproliferative activity and preliminary toxicity studies

New palladium and platinum complexes with bioactive 3,5-diacetyl-1,2,4-triazol bis(4-cyclohexyl thiosemicarbazone) ligand: chemistry, antiproliferative activity and preliminary toxicity studies

Tetranuclear [Rh4(μ-PyS2)2(diolefin)4] Complexes as Building Blocks for New Inorganic Architectures: Synthesis of Coordination Polymers and Heteropolynuclear Complexes with Electrophilic d8and d10Metal Fragments

Synthesis and controlled hydrolysis of organolanthanide complexes with mono- and dianionic benzimidazole-2-thiolate ligands

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Tetranuclear [Rh₄(μ-PyS₂)₂(diolefin)₄] Complexes as Building Blocks for New Inorganic Architectures: Synthesis of Coordination Polymers and Heteropolynuclear Complexes with Electrophilic d⁸and d¹⁰Metal Fragments